CN110104851A - One kind being used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method - Google Patents

One kind being used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method Download PDF

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CN110104851A
CN110104851A CN201910480083.1A CN201910480083A CN110104851A CN 110104851 A CN110104851 A CN 110104851A CN 201910480083 A CN201910480083 A CN 201910480083A CN 110104851 A CN110104851 A CN 110104851A
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water
enters
high density
softening
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李海波
王靖宇
盛宇星
李玉平
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Beijing Saike Kanglun Environmental Science & Technology Co Ltd
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Beijing Saike Kanglun Environmental Science & Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • C—CHEMISTRY; METALLURGY
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    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/07—Preparation from the hydroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • 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
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds

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Abstract

The invention discloses one kind to be used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, and waste water is first carried out level-one softening removal Mg by this method2+And heavy metal ion, level-one soften mud mixture and enter the first high density precipitation unit, obtained supernatant enters secondary softening unit removal Ca2+Secondary softening mud mixture is precipitated into the second high density precipitation unit, supernatant is handled by membranous system, obtained fresh water circulating and recovering, the concentrated water of generation enters chelating resin unit, depth goes removing calcium and magnesium and heavy metal ion, and water outlet enters bipolar membrane electrodialysis unit, and it is 10% sodium hydroxide solution and 8% hydrochloric acid solution that processing, which obtains concentration,；The method achieve recycling for magnesium hydroxide slurry, the usage amount of flue gas desulfurization oxidation magnesium is greatly reduced, soda acid technique is produced using bipolar membrane electrodialysis, while preparing soda ash using carbon dioxide in power-plant flue gas, the resource utilization of salt in waste water is realized, softens medicament without outsourcing.

Description

One kind being used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method
Technical field
The invention belongs to sewage advanced treatment fields, more particularly to one kind to be used for the zero-emission of magnesium oxide method power plant desulfurization wastewater Processing method.
Background technique
The Cl mainly having in the desulfurization wastewater that thermal power plant's magnesium oxide method desulfurization generates containing ion-、SO42-、Na+、Mg2+、 Ca2+, especially Mg2+Content is higher, is typical with high salt, high rigidity waste water.Currently, domestic and international Desulphurization for Coal-fired Power Plant waste water zero Discharge project mostly uses greatly " softening+film concentration+evaporative crystallization " process route.When the above zero-emission project operation, using hydrogen-oxygen The mode for changing the dosing of calcium+soda ash softens, and can generate a large amount of magnesium hydroxide and calcium carbonate mixing sludge, current method of disposal It is that will be filled after above-mentioned mixing sludge filter-press dehydration, since waste water Mg and Ca content is higher, generation sludge quantity is larger, processing cost It is high.The salt of output in vapo(u)rization system, main component are sodium chloride and sodium sulphate, and salt-mixture does not have market that can dissolve, Zhi Nengzuo For fixed-end forces；Sodium chloride and sodium sulphate index after dividing salt are also difficult to meet market demands, and value of the product is low.
It can be seen that current desulfurization wastewater technique of zero discharge solves only discharge of wastewater problem, generated in treatment process A large amount of solid wastes, system operation cost is not only significantly increased, but also resource is not utilized rationally.
Summary of the invention
In view of the above-mentioned problems, the present invention provides one kind to be used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, Even more a kind of recycling processing method, the processing method by softening, high density precipitating, film processing system and chelating resin and Bipolar membrane electrodialysis combines, and coordinates mutually, finally not only realizes the zero-emission of waste water, and realize the reasonable benefit of resource With.
To achieve this purpose, the present invention adopts the following technical scheme:
One kind being used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, which is characterized in that the waste water is first carried out one Grade softening removal Mg2+ and heavy metal ion, level-one soften mud mixture and enter the first high density precipitation unit, and what is obtained is upper Clear liquid enters secondary softening unit removal Ca2+, and secondary softening mud mixture is precipitated into the second high density precipitation unit, on Clear liquid is handled by membranous system, and obtained fresh water circulating and recovering, the concentrated water of generation enters chelating resin unit, and depth removes removing calcium and magnesium And heavy metal ion, water outlet enter Bipolar Membrane
The film processing system includes sequentially connected ultrafiltration, nanofiltration and film upgrading unit.
The film upgrading unit includes one or both of reverse osmosis, electrodialysis combination.
Level-one softening adds sodium hydroxide solution, NaOH solution and Mg2+Molar ratio be 2:1-3:1, residence time 10- 30min。
Level-one softens mud mixture and precipitates into the first high density precipitation unit, obtained Mg(OH)2Sediment slurry is returned For flue gas desulfurization, the sulfur dioxide in power-plant flue gas, sedimentation time 2h-5h are absorbed.
First high density precipitating supernatant enters secondary softening unit, adds sodium carbonate liquor, Na2CO3Solution and Ca2+'s Molar ratio is 1:1-1.5:1, residence time 10-30min.
Secondary softening mud mixture enters the second high density precipitation unit, obtained CaCO3Sludge enters Treatment of Sludge Unit, sedimentation time 2h-5h.
PH is adjusted to enter film process system after 7-8 by the water outlet of the second high density precipitation unit supernatant by adding hydrochloric acid solution System.
Into after film processing system, the NF concentrated water reuse rich in sodium sulphate generated by nanofiltration is generated in flue gas desulfurization Enter film upgrading unit rich in sodium chloride fresh water；The fresh water that the film upgrading unit generates as recirculated water reuse, generation it is dense Water enters chelating resin unit, and depth goes the heavy metal ion such as removing calcium and magnesium, uses the sum of water heavy metal ion < 0.1mg/L.
Chelating resin water outlet enters bipolar membrane electrodialysis unit, and preparing concentration is 10% sodium hydroxide solution and 8% hydrochloric acid Solution；The sodium hydroxide solution can be back to level-one pliable cell and secondary softening unit or be used to prepare soda ash.
Compared with prior art, the invention has the following advantages:
(1) the invention discloses magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, this method is realized by fractional precipitation Recycling for magnesium hydroxide slurry, is greatly reduced the usage amount of flue gas desulfurization oxidation magnesium, effectively reduces at power-plant flue gas Manage cost；
(2) soda acid technique is produced using bipolar membrane electrodialysis, realizes the money for realizing salt in waste water while power plant effluent zero-emission Sourceization utilizes, and produced soda acid reuse is used for water treatment system, while preparing soda ash using carbon dioxide in power plant's flue gas, is not necessarily to Outsourcing softens medicament, effectively reduces cost for wastewater treatment.
Detailed description of the invention
Fig. 1 is magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method flow chart of the present invention.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting Embodiment it is as follows:
As shown in Figure 1, a kind of be used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, waste water is first subjected to level-one softening Remove Mg2+ and heavy metal ion, level-one softens mud mixture and enters the first high density precipitation unit, obtained supernatant into Enter secondary softening unit removal Ca2+, secondary softening mud mixture precipitates into the second high density precipitation unit, and supernatant passes through Membranous system processing, obtained fresh water circulating and recovering, the concentrated water of generation enter chelating resin unit, and depth removes removing calcium and magnesium and heavy metal Ion, water outlet enter bipolar membrane electrodialysis unit, and it is 10% sodium hydroxide solution and 8% hydrochloric acid solution that processing, which obtains concentration,.
Wherein, film processing system includes sequentially connected ultrafiltration, nanofiltration and film upgrading unit, and film upgrading unit includes reverse osmosis Thoroughly, one or both of electrodialysis is combined；Level-one, which softens, adds sodium hydroxide solution, and the molar ratio of NaOH solution and Mg2+ are 2:1-3:1, that is, 2:1,2.1:1,2.2:1,2.3:1,2.4:1,2.5:1,2.6:1,2.7:1,2.8:1,2.9:1,3:1, when stop Between be 10-30min, i.e. 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min、21min、22min、23min、24min、25min、26min、27min、28min、29min、30min。
Level-one softens mud mixture and precipitates into the first high density precipitation unit, obtained Mg(OH)2Sediment slurry is returned For flue gas desulfurization, the sulfur dioxide in power-plant flue gas, sedimentation time 2h-5h, 2h, 3h, 4h, 5h are absorbed.
First high density precipitating supernatant enters secondary softening unit, adds sodium carbonate liquor, sodium carbonate liquor derives from Soda ash preparation unit in system, Na2CO3Solution and Ca2+Molar ratio be 1:1-1.5:1,1.1:1,1.2:1,1.3:1,1.4: 1,1.5:1, residence time 10-30min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min、19min、20min、21min、22min、23min、24min、25min、26min、27min、28min、29min、 30min。
Secondary softening mud mixture enters the second high density precipitation unit, obtained CaCO3Sludge enters Treatment of Sludge Unit, sedimentation time 2h-5h, 2h, 3h, 4h, 5h.
PH is adjusted to enter film process system after 7-8 by the water outlet of the second high density precipitation unit supernatant by adding hydrochloric acid solution System.
Into after film processing system, the NF concentrated water reuse rich in sodium sulphate generated by nanofiltration is generated in flue gas desulfurization Enter film upgrading unit rich in sodium chloride fresh water；The fresh water that the film upgrading unit generates as recirculated water reuse, generation it is dense Water enters chelating resin unit, and depth goes the heavy metal ion such as removing calcium and magnesium, uses the sum of water heavy metal ion < 0.1mg/L.
Chelating resin water outlet enters bipolar membrane electrodialysis unit, and preparing concentration is 10% sodium hydroxide solution and 8% hydrochloric acid Solution；Wherein sodium hydroxide solution can be back to level-one pliable cell and secondary softening unit or be used to prepare soda ash.
Embodiment 1
Certain magnesium oxide method power plant desulfurization wastewater water quality is as shown in table 1, unit, mg/L
Waste water initially enters level-one pliable cell, adds a large amount of Mg in sodium hydroxide solution and water2+Generate Mg(OH)2Precipitating, Micro other heavy metal ion such as Cu, As, Pb etc. in water removal are removed simultaneously, and sodium hydroxide is from Bipolar Membrane electric osmose in system Unit is analysed, wherein NaOH and Mg2+Molar ratio be 2:1, residence time 20min.
Level-one softening mud mixture enters high density precipitation unit precipitating, obtained Mg(OH)2Sediment slurry is back to Flue gas desulfurization absorbs the sulfur dioxide in power-plant flue gas, sedimentation time 3h, high density precipitating water outlet Mg2+It is reduced to 20mg/L Below.
High density precipitating supernatant enters secondary softening unit, adds the Ca in sodium carbonate liquor and water2+Generate CaCO3It is heavy It forms sediment, sodium carbonate derives from soda ash preparation unit in system, wherein Na2CO3With Ca2+Molar ratio be 1:1, the residence time is 20min。
Secondary softening mud mixture enters high density precipitation unit precipitating, obtained CaCO3Sludge enters Treatment of Sludge Unit, sedimentation time 4h, potassium permanganate composites are discharged Ca2+ 30mg/L or less.
High density precipitating supernatant water outlet adjusts ph to 7-8 by adding hydrochloric acid, goes into ultrafiltration system outstanding in water removal After floating object, colloid, divide salt into nanofiltration system.Hydrochloric acid used is the hydrochloric acid that the bipolar membrane electrodialysis unit in system generates.
For the NF concentrated water reuse rich in sodium sulphate that nanofiltration generates in flue gas desulfurization, nanofiltration, which is generated, enters film rich in sodium chloride fresh water Upgrading unit.The film upgrading unit is concentrated using high pressure reverse osmosis process.
The fresh water that film concentration generates is as recirculated water reuse, and the concentrated water sodium chloride content of generation is 13%, into chelating resin Unit goes the heavy metal ion such as removing calcium and magnesium, out the sum of water heavy metal ion < 0.1mg/L.
Chelating resin water outlet enters bipolar membrane electrodialysis unit, and preparing concentration is about 10% sodium hydroxide solution and 8% salt Acid solution.
Sodium hydroxide solution a part is back to level-one pliable cell and for Membrane cleaning, and it is single that a part enters soda ash preparation Member, the soda ash preparation unit are passed through after processing rich in CO2Power-plant flue gas, control CO2Molar ratio with NaOH is 1:2, raw At sodium carbonate liquor.Hydrochloric acid solution be back to potassium permanganate composites water outlet after secondary softening adjust ph to it is neutral and for film it is clear It washes.
Embodiment 2
Certain magnesium oxide method power plant desulfurization wastewater water quality is as shown in table 1, unit, mg/L
Waste water initially enters level-one pliable cell, adds a large amount of Mg in sodium hydroxide solution and water2+Generate Mg(OH)2Precipitating, Micro other heavy metal ion such as Cu, As, Pb etc. in water removal are removed simultaneously, and sodium hydroxide is from Bipolar Membrane electric osmose in system Unit is analysed, wherein NaOH and Mg2+Molar ratio be 2.5:1, residence time 30min.
Level-one softening mud mixture enters high density precipitation unit precipitating, obtained Mg(OH)2Sediment slurry is back to Flue gas desulfurization absorbs the sulfur dioxide in power-plant flue gas, sedimentation time 4h, high density precipitating water outlet Mg2+It is reduced to 20mg/L Below.
High density precipitating supernatant enters secondary softening unit, adds the Ca in sodium carbonate liquor and water2+Generate CaCO3It is heavy It forms sediment, sodium carbonate derives from soda ash preparation unit in system, wherein Na2CO3With Ca2+Molar ratio be 1:1, the residence time is 30min。
Secondary softening mud mixture enters high density precipitation unit precipitating, obtained CaCO3Sludge enters Treatment of Sludge Unit, sedimentation time 5h, potassium permanganate composites are discharged Ca2+ 30mg/L or less.
High density precipitating supernatant water outlet adjusts ph to 7-8 by adding hydrochloric acid, goes into ultrafiltration system outstanding in water removal After floating object, colloid, divide salt into nanofiltration system.Hydrochloric acid used is the hydrochloric acid that the bipolar membrane electrodialysis unit in system generates.
For the NF concentrated water reuse rich in sodium sulphate that nanofiltration generates in flue gas desulfurization, nanofiltration, which is generated, enters film rich in sodium chloride fresh water Upgrading unit.The film upgrading unit is reverse osmosis using high pressure and electrodialysis group technology is concentrated.
The fresh water that film concentration generates is as recirculated water reuse, and the concentrated water sodium chloride content of generation is 15%, into chelating resin Unit goes the heavy metal ion such as removing calcium and magnesium, out the sum of water heavy metal ion < 0.1mg/L.
Chelating resin water outlet enters bipolar membrane electrodialysis unit, and preparing concentration is about 10% sodium hydroxide solution and 8% salt Acid solution.
Sodium hydroxide solution a part is back to level-one pliable cell and for Membrane cleaning, and it is single that a part enters soda ash preparation Member, the soda ash preparation unit are passed through after processing rich in CO2Power-plant flue gas, control CO2Molar ratio with NaOH is 1:2, raw At sodium carbonate liquor.Hydrochloric acid solution be back to potassium permanganate composites water outlet after secondary softening adjust ph to it is neutral and for film it is clear It washes.
Embodiment 3
Certain magnesium oxide method power plant desulfurization wastewater water quality is as shown in table 1, unit, mg/L
Waste water initially enters level-one pliable cell, adds a large amount of Mg in sodium hydroxide solution and water2+Generate Mg(OH)2Precipitating, Micro other heavy metal ion such as Cu, As, Pb etc. in water removal are removed simultaneously, and sodium hydroxide is from Bipolar Membrane electric osmose in system Unit is analysed, wherein NaOH and Mg2+Molar ratio be 3:1, residence time 30min.
Level-one softening mud mixture enters high density precipitation unit precipitating, obtained Mg(OH)2Sediment slurry is back to Flue gas desulfurization absorbs the sulfur dioxide in power-plant flue gas, sedimentation time 4h, high density precipitating water outlet Mg2+It is reduced to 20mg/L Below.
High density precipitating supernatant enters secondary softening unit, adds the Ca in sodium carbonate liquor and water2+Generate CaCO3It is heavy It forms sediment, sodium carbonate derives from soda ash preparation unit in system, wherein Na2CO3With Ca2+Molar ratio be 1.2:1, the residence time is 30min。
Secondary softening mud mixture enters high density precipitation unit precipitating, obtained CaCO3Sludge enters Treatment of Sludge Unit, sedimentation time 5h, potassium permanganate composites are discharged Ca2+30mg/L or less.
High density precipitating supernatant water outlet adjusts ph to 7-8 by adding hydrochloric acid, goes into ultrafiltration system outstanding in water removal After floating object, colloid, divide salt into nanofiltration system.Hydrochloric acid used is the hydrochloric acid that the bipolar membrane electrodialysis unit in system generates.
For the NF concentrated water reuse rich in sodium sulphate that nanofiltration generates in flue gas desulfurization, nanofiltration, which is generated, enters film rich in sodium chloride fresh water Upgrading unit.The film upgrading unit is reverse osmosis using high pressure and electrodialysis group technology is concentrated.
The fresh water that film concentration generates is as recirculated water reuse, and the concentrated water sodium chloride content of generation is 18%, into chelating resin Unit goes the heavy metal ion such as removing calcium and magnesium, out the sum of water heavy metal ion < 0.1mg/L.
Chelating resin water outlet enters bipolar membrane electrodialysis unit, and preparing concentration is about 10% sodium hydroxide solution and 8% salt Acid solution.
Sodium hydroxide solution a part is back to level-one pliable cell and for Membrane cleaning, and it is single that a part enters soda ash preparation Member, the soda ash preparation unit are passed through after processing rich in CO2Power-plant flue gas, control CO2Molar ratio with NaOH is 1:2, raw At sodium carbonate liquor.Hydrochloric acid solution be back to potassium permanganate composites water outlet after secondary softening adjust ph to it is neutral and for film it is clear It washes.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. one kind is used for magnesium oxide method power plant desulfurization wastewater Zero discharge treatment method, which is characterized in that first carry out the waste water Level-one softening removal Mg2+And heavy metal ion, level-one soften mud mixture and enter the first high density precipitation unit, what is obtained is upper Clear liquid enters secondary softening unit removal Ca2+, secondary softening mud mixture into the second high density precipitation unit precipitate, supernatant Liquid is handled by membranous system, obtained fresh water circulating and recovering, and the concentrated water of generation enters chelating resin unit, depth go removing calcium and magnesium and Heavy metal ion, water outlet enter bipolar membrane electrodialysis unit, and it is that 10% sodium hydroxide solution and 8% hydrochloric acid are molten that processing, which obtains concentration, Liquid.
2. processing method as described in claim 1, which is characterized in that the film processing system include sequentially connected ultrafiltration, Nanofiltration and film upgrading unit.
3. processing method as claimed in claim 2, which is characterized in that the film upgrading unit includes in reverse osmosis, electrodialysis One or two kinds of combinations.
4. processing method as claimed in claim 3, which is characterized in that level-one softening adds sodium hydroxide solution, NaOH solution With Mg2+Molar ratio be 2:1-3:1, residence time 10-30min.
5. processing method as claimed in claim 4, which is characterized in that it is heavy into the first high density that level-one softens mud mixture Shallow lake unit precipitating, obtained Mg(OH)2Sediment slurry is back to flue gas desulfurization, absorbs the sulfur dioxide in power-plant flue gas, precipitating Time is 2h-5h.
6. processing method as claimed in claim 5, which is characterized in that the first high density precipitating supernatant enters secondary softening list Member adds sodium carbonate liquor, Na2CO3Solution and Ca2+Molar ratio be 1:1-1.5:1, residence time 10-30min.
7. processing method as claimed in claim 6, which is characterized in that secondary softening mud mixture is heavy into the second high density Shallow lake unit, obtained CaCO3Sludge enters sludge treating block, sedimentation time 2h-5h.
8. processing method as claimed in claim 7, which is characterized in that the water outlet of the second high density precipitation unit supernatant passes through throwing Enter film processing system after adding hydrochloric acid solution that pH is adjusted to 7-8.
9. processing method as claimed in claim 8, which is characterized in that after entering film processing system, generated by nanofiltration NF concentrated water reuse rich in sodium sulphate generates in flue gas desulfurization and enters film upgrading unit rich in sodium chloride fresh water；The film concentration is single For the fresh water that member generates as recirculated water reuse, the concentrated water of generation enters chelating resin unit, depth go the heavy metals such as removing calcium and magnesium from Son uses the sum of water heavy metal ion < 0.1mg/L.
10. processing method as claimed in claim 9, which is characterized in that chelating resin water outlet enters bipolar membrane electrodialysis unit, Preparing concentration is 10% sodium hydroxide solution and 8% hydrochloric acid solution；The sodium hydroxide solution can be back to level-one pliable cell With secondary softening unit or be used to prepare soda ash.
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CN110422965A (en) * 2019-08-26 2019-11-08 中国石油化工股份有限公司 The processing method and processing system of flue gas desulfurization waste-water and application
CN110746008A (en) * 2019-10-29 2020-02-04 南京友智科技有限公司 Wastewater treatment system
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CN112479421A (en) * 2020-11-10 2021-03-12 西安西热水务环保有限公司 High-hardness wastewater softening and resource recycling system and method
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US11502323B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell and methods of use thereof
US11502322B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell with heat pump
US11563229B1 (en) 2022-05-09 2023-01-24 Rahul S Nana Reverse electrodialysis cell with heat pump
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US11699803B1 (en) 2022-05-09 2023-07-11 Rahul S Nana Reverse electrodialysis cell with heat pump
US11855324B1 (en) 2022-11-15 2023-12-26 Rahul S. Nana Reverse electrodialysis or pressure-retarded osmosis cell with heat pump
CN116891242A (en) * 2023-09-11 2023-10-17 杭州科膜水处理工程有限公司 Treatment method for short-process treatment of industrial waste salt

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