CN107381881A - The method of wastewater treatment and processing unit of desulfurization wastewater zero-emission - Google Patents
The method of wastewater treatment and processing unit of desulfurization wastewater zero-emission Download PDFInfo
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- CN107381881A CN107381881A CN201710833227.8A CN201710833227A CN107381881A CN 107381881 A CN107381881 A CN 107381881A CN 201710833227 A CN201710833227 A CN 201710833227A CN 107381881 A CN107381881 A CN 107381881A
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- desulfurization wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 91
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 76
- 230000023556 desulfurization Effects 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 33
- 238000005189 flocculation Methods 0.000 claims abstract description 25
- 230000016615 flocculation Effects 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 23
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000001994 activation Methods 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 27
- 230000004913 activation Effects 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000011229 interlayer Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000013043 chemical agent Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011195 cermet Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000035515 penetration Effects 0.000 claims 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- -1 electric power Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012954 risk control Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—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
- C02F5/02—Softening water by precipitation of the hardness
Abstract
The present invention relates to a kind of method of wastewater treatment and processing unit of desulfurization wastewater zero-emission, including pretreatment unit, film process unit, pretreatment unit includes flocculation basin and the chemical cycle that is connected with flocculation basin is granulating fluidized bed, is gone firmly for removing in waste water suspension and softening；Film process unit includes scale inhibiting cleaner and the nano filter membrance device being connected with scale inhibiting cleaner, for first being activated to desulfurization wastewater, to realize antiscale, scale removal purpose, then by Cl—By desulfurization wastewater reuse after being separated from desulfurization wastewater, and Cl—Then it is used as chemicals production raw material.The method of wastewater treatment and processing unit of the desulfurization wastewater zero-emission of the present invention, can not only reuse be carried out to the desulfurization wastewater after processing, while by Ca2+、Mg2+、Cl—Recycled Deng separation has been carried out from desulfurization wastewater, not only realize the zero-emission of desulfurization wastewater, reduce the pollution to environment, also a saving resource, effective utilization has been carried out to resource, and whole processing procedure is green, non-secondary pollution.
Description
Technical field
The present invention relates to environmental technology field, more particularly to a kind of method of wastewater treatment of desulfurization wastewater zero-emission and processing
Device.
Background technology
China is the poor and in short supply country of a water resource, development and process of industrialization with China's economic construction
Accelerate, industrial water demand is increased substantially, and the discharge capacity of industrial wastewater is consequently increased, and the imbalance between supply and demand of water resource will more
Add protrusion.Therefore, for the problem such as water resource critical shortage and water utilization rate be low, what country newly promulgated《Water pollution is prevented
Control action plan》In industrial wastewater pollution preventing and treating, improve water-use efficiency, pollutant emission factor, environmental risk control etc.
Aspect proposes more strict requirements, and this, which allows for the key industrys such as coal, electric power, steel, chemical industry, needs to widely popularize work
Industry cycling utilization of wastewater technology, to reach the purpose of " zero-emission ".
Wastewater zero discharge is the concept proposed by American-European economically developed country the 1970s, is one for work
Industry waste water carries out the comprehensive application technology of complex process." zero-emission " refer to ad infinitum reduce pollutant and can source emission until
The activity for being zero, i.e., caused industrial wastewater can be returned all after proper technology is handled in process of production for all kinds of enterprises
With any waste water will not be discharged into outside water body environment.
In sulfur removal technology, a certain amount of waste water is inevitably produced.The water quality of desulfurization wastewater is complex, mainly
Composition is dust and desulfurization product (CaSO4And CaSO3), for pH value typically in the range of 4~6.5, concentration of suspension is high, contains
A large amount of Ca2+、Mg2+Cation and SO4 2—、Cl—、F—Deng anion, TDS is typically between 25000-60000mg/L, wherein Cl—
Content contains a small amount of Hg typically between 5000-20000mg/L2+、Cr6+、Cd2+、Pb2+Etc. heavy metal ion, to ring
The harm in border is extremely serious.
Desulfurization wastewater technique of zero discharge relates generally to two stages of Chemical Pretreatment and advanced treating at present.Chemical Pretreatment
For removing F in desulfurization wastewater—、Ca2+、Mg2+With part heavy metal ion, advanced treating is used to remove the salt in desulfurization wastewater
Divide and separate out salt crystallization and recycle.The Chemical Pretreatment stage mainly adds special flocculant, scale inhibition into desulfurization wastewater
Agent, softening agent and other adjuvants, make the calcium in water, magnesium ion, heavy metal ion and corrosive salt and medicament formed it is heavy
Shallow lake is peeled off from water, or formation complex compound increases its solubility in water, so as to realize the purpose of removal.But at the waste water
The medicament delivery amount of reason method is very big, and cost is high, and can produce substantial amounts of sludge, brings secondary pollution problems；Can also simultaneously
New material is introduced, new foreign ion can be produced in water, this will be that follow-up processing brings the problem of new.
The advanced treating stage mainly applies membrane filtration technique and evaporative crystallization technique, and evaporative crystallization technique typically uses more
Imitate evaporator.Although multi-effect evaporator Technical comparing is ripe, application is wider, but part energy consumption is reduced, but in desulfurization wastewater
Containing substantial amounts of salt, the corrosivity of salt solution is extremely strong under high temperature, therefore higher to multi-effect evaporator equipment and material choice requirement,
This results in increasing for cost of equipment, so that Installed capital cost is high；And need to expend substantial amounts of electric energy in the process of running
And water vapour so that operating cost is higher；In addition, the crystal salt that evaporative crystallization finally gives is salt-mixture, it is difficult to is separated, inconvenience
In reusing, therefore salt-mixture will be used as hazardous waste to exist, if must not be serious when that will bring to mixing salt treatment
Pollution.
In summary, Chemical Pretreatment and advanced treating stage exist during desulfurization wastewater zero discharge treatment
Deficiency, therefore for the water quality characteristicses of desulfurization wastewater, exploring the method and system for developing new desulfurization wastewater zero-emission has weight
The Engineering Guidance meaning wanted.
The content of the invention
In order to solve the above problems, the invention provides a kind of method of wastewater treatment of desulfurization wastewater zero-emission and processing dress
To put, the method for wastewater treatment and processing unit of the desulfurization wastewater zero-emission not only can carry out reuse to the desulfurization wastewater after processing,
Simultaneously by Ca2+、Mg2+、Cl—Recycled Deng separation has been carried out from desulfurization wastewater, realize the zero-emission of desulfurization wastewater, reduced
Pollution to environment, also a saving resource, carry out to resource effective utilization, and whole processing procedure is green, without two
Secondary pollution.
The technical solution adopted by the present invention is：A kind of method of wastewater treatment of desulfurization wastewater zero-emission, comprises the following steps：
A, pre-process：Flocculation aid or flocculant are added into desulfurization wastewater, flocculation, sedimentation, collect supernatant after being well mixed
Liquid；
B, softening is gone hard：Chemical agent and crystal seed are added into supernatant, makes the Ca in supernatant2+、Mg2+Ion is formed
CaCO3With Mg (OH)2Crystal separates out, and reduces the hardness in supernatant；
C, film pre-treatment：Waste water after being gone firmly to softening using activation ceramics carries out activation process, realizes and waste water is removed
Dirty, molten dirt, scale inhibition, the effect of sterilization；And activated delay ceramics make activated water maintain the state of activation；
D, film process：Waste water after step c processing is obtained into secondary water and strong brine through film process, strong brine is as benefit
Water-filling reuse, secondary water are used as chemicals production raw material.
As the further restriction to above-mentioned technical proposal, chemical agent described in step b is sodium hydroxide.
As the further restriction to above-mentioned technical proposal, contain lithium, rubidium, caesium, beryllium element in activation ceramics described in step c
In one or more；It is described activation delay ceramics in containing sodium, magnesium, phosphorus, iron, iodine, Zn-ef ficiency one or more.
As the further restriction to above-mentioned technical proposal, film process described in step d is to be carried out using NF membrane at filtering
Reason.
A kind of wastewater treatment equipment of desulfurization wastewater zero-emission, at the waste water for desulfurization wastewater zero-emission described above
Reason method, including pretreatment unit, the film process unit that is connected with pretreatment unit；
The pretreatment unit includes flocculation basin and the chemicrystallization being connected with flocculation basin circulation is granulating fluidized bed；It is described
The bottom of flocculation basin is provided with water inlet and sewage draining exit, and top is provided with purified liquor outlet, and water inlet passes through the pipeline with the first water pump
Be connected with the desulfurization wastewater output end in desulphurization system, purified liquor outlet with chemical cycle is granulating fluidized bed is connected；The chemistry follows
The granulating fluidized bed bottom of ring is sequentially provided with dosing mouth, crystal seed dispensing port and particulate emission mouth, and top exports provided with overflow；
The film process unit includes scale inhibiting cleaner and the reverse osmosis membrane apparatus being connected with scale inhibiting cleaner；The resistance
Left chamber and right chamber room are divided into by plate inside dirty descaler, the plate has space, the left side with scale inhibiting cleaner bottom
The inwall of chamber is provided with nanometer antiscale cermet coating, and the inwall of the right chamber room is provided with activation delay nano-ceramic layer,
And water inlet is set at the top of the left chamber, in the right chamber roof, delivery port is set；The scale inhibiting cleaner water inlet
The overflow outlet granulating fluidized bed with chemical cycle is connected, and delivery port is connected with nano filter membrance device；The nano filter membrance device it is defeated
Going out end includes divalent salts concentrate output end and monovalent salt penetrating fluid output end, divalent salts concentrate output end and reuse tank phase
Even, monovalent salt penetrating fluid output end connection infiltration flow container.
As the further restriction to above-mentioned technical proposal, the chemical cycle it is granulating fluidized bed in be provided with cylinder, institute
Stating has interlayer between cylinder and the granulating fluidized bed inwall of chemical cycle, and the both ends open of interlayer.
As the further restriction to above-mentioned technical proposal, the flocculation basin water inlet sets pressure gauge and fluid flow
Meter.
Using above-mentioned technology, the advantage of the invention is that：
The method of wastewater treatment and processing unit of desulfurization wastewater zero-emission of the present invention, flocculation sediment is handled, changed
Learning crystallization granulation softening goes hard processing, activation process, membrane technology to be combined, and being granulated by chemicrystallization can effectively go in water removal
Hardness (Ca2+、Mg2+), while after being activated using activation ceramics to water, through NF membrane by Cl—After being separated from desulfurization wastewater
Desulfurization wastewater can be made to carry out reuse, effectively prevent the Cl in desulfurization wastewater—Corrosion to equipment, while the Cl isolated—
It can be achieved to recycle.During desulfurization wastewater is handled, it is not necessary to outwards discharge any liquid, part water can industry time
With, another part realizes recycling, and solid waste can also be used for brickmaking industry, truly realize desulfurization
The zero-emission of waste water, and whole processing procedure is green, pollution-free.
The granulating fluidized bed setting of chemical cycle of the present invention, the Ca that can be gone by chemicrystallization comminution granulation in water removal2+、
Mg2+, make Ca2+、Mg2+Generate CaCO3With Mg (OH)2Crystal, and be attached to seed surface and form bulky grain crystal seed, surface attachment has
CaCO3With Mg (OH)2The bulky grain crystal seed of crystal can use as the raw material of desulphurization system, it is turned waste into wealth, while also make
Resource has obtained great utilization.
The setting of scale inhibiting cleaner of the present invention, the nanometer antiscale cermet coating in scale inhibiting cleaner left chamber can be right
Water carries out activation process, the hydrogen bond angle of hydrone is substantially broadened, and is combined so as to form stronger molecule, reduces the surface of water
Tension force, change the pH value of water, water is reached the pH pH-values balance between 7-8；Simultaneously by the change of hydrogen bond, deposit in water
Calcium ion break original growth sequence, and be not likely to produce adhesion condition, so as to avoid scale formation, also play molten dirt
Effect；In addition, the activation delay nano-ceramic layer in scale inhibiting cleaner right chamber room can also make activated water continue to the state of activation,
Duration is activated up to 48 hours, so as to be not in fouling in the subsequent treatment of water, in order to avoid influence the normal operation of follow-up equipment.
The setting of NF membrane of the present invention, the dissolubility inorganic salts in desulfurization wastewater can be effectively handled, in inorganic salts
Monovalent ion separated with divalent ion, so as to realize SO in desulfurization wastewater4 2—、Cl—Separation, with SO4 2—Solution
As technique Water circulation, and carry Cl—Penetrating fluid can then to concentrate be saturated brine to as bactericide or other products；
Simultaneously by Cl—Separated from desulfurization wastewater, also effectively prevent Cl—The corrosion of equipment is caused into equipment, influences equipment
Service life.
Brief description of the drawings
Fig. 1 is the connection diagram of the wastewater treatment equipment of desulfurization wastewater zero-emission of the embodiment of the present invention.
In figure：1- flocculation basins；2- chemical cycles are granulating fluidized bed；The water pumps of 3- first；4- scale inhibiting cleaners；5- NF membranes fill
Put；6- reuse tanks；7- permeates flow container.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is described in further detail.
The present embodiment is related to a kind of method of wastewater treatment of desulfurization wastewater zero-emission, and the method for wastewater treatment gives up for desulfurization
The wastewater treatment equipment of water zero discharge, it is also available while waste water recycling is realized to be post-processed to desulfurization wastewater
Chemicals production raw material.As shown in Figure 1, the wastewater treatment equipment of the desulfurization wastewater zero-emission includes pretreatment unit, located with pre-
The connected film process unit of reason unit and what is be connected with film process unit divide salt unit.Pretreatment unit include flocculation basin 1 and
The chemicrystallization circulation granulating fluidized bed 2 being connected with flocculation basin 1；The bottom of the flocculation basin 1 is provided with water inlet and sewage draining exit, top
Portion is provided with purified liquor outlet, and water inlet is connected by the pipeline with the first water pump 3 with the desulfurization wastewater output end in desulphurization system,
Pressure gauge and fluid flowmeter, purified liquor outlet is set to be connected with chemical cycle granulating fluidized bed 2 in water inlet simultaneously.
The bottom of chemical cycle granulating fluidized bed 2 is sequentially provided with dosing mouth, crystal seed dispensing port and particulate emission mouth, top and set
There is overflow outlet, dosing mouth is used to add into chemical cycle granulating fluidized bed 2 to be easy to and the Ca in waste water2+、Mg2+Deng generation
The chemical agent of precipitation, crystal seed dispensing port is used to add crystal seed into chemical cycle granulating fluidized bed 2, so that Ca2+、Mg2+Deng with
The sediment of chemical agent reaction generation is attached to seed surface and forms seed particles.In in chemical cycle granulating fluidized bed 2
Portion is provided with cylinder, has interlayer, and the both ends open of interlayer between cylinder and granulating fluidized bed 2 inwall of chemical cycle, it is therefore an objective to
The crystal seed in granulating fluidized bed 2 cylinder of chemical cycle is being moved to from bottom to top with current behind top, fallen after rise in interlayer
Crystallization process is continued to participate in granulating fluidized bed 2 bottom of chemical cycle, is so moved in circles, until generating seed particles from particle
Floss hole is discharged.
Film process unit includes scale inhibiting cleaner 4 and the nano filter membrance device 5 being connected with scale inhibiting cleaner 4, for pre- place
Waste water after reason carries out filtration treatment, to realize the desalination of desulfurization wastewater and concentration.It is divided into inside scale inhibiting cleaner 4 by plate
Left chamber and right chamber room, plate have space with the bottom of scale inhibiting cleaner 4, water inlet are set at the top of left chamber, in right chamber roof
Delivery port is set；The water inlet of scale inhibiting cleaner 4 is connected with the overflow outlet of chemical cycle granulating fluidized bed 2, so that through chemistry
The left chamber that the desulfurization wastewater after granulating fluidized bed 2 softening is gone firmly enters scale inhibiting cleaner 4 is circulated, passes through plate and scale inhibition afterwards
Space between the bottom of descaler 4 enters right chamber room.Made pottery in the inwall of the left chamber of scale inhibiting cleaner 4 provided with nanometer antiscale metal
Enamel coating, the inwall of right chamber room are provided with activation delay nano-ceramic layer, for carrying out activation process to desulfurization wastewater, can play resistance
Dirt, scale removal, the effect of sterilization, therefore can have certain protective effect to follow-up film device, it can effectively extend the use of film
Life-span.The delivery port of scale inhibiting cleaner 4 is connected with nano filter membrance device 5, nano filter membrance device 5 can effectively to the monovalence in inorganic salts from
Son is separated with divalent ion, so as to realize SO4 in desulfurization wastewater2—、Cl—Separation so that Cl—Divide from desulfurization wastewater
By desulfurization wastewater reuse from after, the Cl in desulfurization wastewater is effectively avoided—Corrosion to equipment.The output end bag of nano filter membrance device 5
Divalent salts concentrate output end and monovalent salt penetrating fluid output end are included, divalent salts concentrate output end is connected with reuse tank 6, reuse
SO4 in pond 62—Concentrate is as technique Water circulation；And monovalent salt penetrating fluid output end is connected with infiltration flow container 7, flow container is permeated
Cl in 7—Penetrating fluid is to as chemicals production raw material.
The wastewater treatment equipment of desulfurization wastewater zero-emission described above, at the waste water available for following desulfurization wastewater zero-emission
Reason method, specific method comprise the following steps：
A, pre-process：Flocculation aid is added into desulfurization wastewater or flocculant, the preferred polyacrylamide of flocculant, flocculation aid are excellent
Lime is selected, flocculation, sedimentation, collect supernatant after being well mixed.Wherein, the pH of desulfurization wastewater can be adjusted by adding flocculation aid lime
, can be by the suspension in desulfurization wastewater, part Ca to 6 or so2+、Mg2+, partial organic substances, the pollution factor such as COD, BOD remove
Fall.Meanwhile the sludge for settling to obtain can discharge, recycled after carrying out subsequent treatment.
B, softening is gone hard：30% NaOH solution and crystal seed is added into supernatant, makes NaOH solution quick with supernatant
Mixing, while crystal seed is in fluidized state under flow action.In flow process, the NaOH and HCO in water3—And Ca2+、Mg2+
Following reaction occurs：
NaOH→OH—+Na+
OH—+Mg2+→Mg(OH)2
OH—+HCO3 —→CO3 2—+H2O, CO3 2—+Ca2+→CaCO3
Therefore, the Ca in supernatant2+、Mg2+Ion forms CaCO with NaOH3With Mg (OH)2Crystal simultaneously separates out, the Mg of precipitation
(OH)2And CaCO3Crystal is constantly attached to tiny seed surface, and tiny crystal seed passes through Mg (OH)2And CaCO3Crystallization
Constantly grow up, the crystal seed of bulky grain is under, and short grained crystal seed is upper.As the Mg (OH) crystallized in seed particles2And CaCO3Matter
When amount reaches more than the 98% of particle gross mass, then seed particles are discharged, at the same time, crystal seed fed.So follow
Ring is reciprocal, the Ca in water2+、Mg2+The overwhelming majority is with CaCO3With Mg (OH)2Form crystallize out and be attached to seed surface, from
And it is reduced the hardness in supernatant.More than 90% Ca is can remove by this method2+, the clearance of total hardness reaches 70-
80%, and without any discharge of wastewater, by CaCO3With Mg (OH)2The bulky grain crystal seed that crystal is attached to seed surface formation can conduct
The raw material of desulphurization system use, and it is turned waste into wealth, while resource has been obtained great utilization.
C, film pre-treatment：Waste water after being gone firmly to softening using activation ceramics carries out activation process, contains in activation ceramics
One or more in lithium, rubidium, caesium, beryllium element, the activation ceramics can make the hydrogen bond angle of water broaden, so as to form stronger point
Son combines, and so can effectively adjust the acidity and basicity of water, water is reached the pH pH-values balance between 7-8；While by
The change of hydrogen bond, calcium ion present in water has broken original growth sequence and has been not likely to produce adhesion condition, so as to avoid sending out
Raw scale formation, also play molten dirt, scale removal, the effect of sterilization.Then, activated delay ceramics make activated water maintain activation shape
State, activation delay ceramics in containing sodium, magnesium, phosphorus, iron, iodine, Zn-ef ficiency one or more, the activation delay ceramics can make activation
Water continues to the state of activation, and activation duration is up to 48h.
D, film process：Waste water after step c processing is handled through NF membrane to obtain secondary water and strong brine, wherein
Strong brine is SO4 2—Concentrate, secondary water Cl—Penetrating fluid.SO4 2—Concentrate, which is used as, supplements Water circulation, and Cl—Penetrating fluid is then
Can be concentrated into being used as bactericide after saturated brine or used as other products.Meanwhile by the Cl in desulfurization wastewater—Isolate
Come, also effectively prevent desulfurization wastewater Cl in reuse—The corrosion of equipment is caused into equipment, influences the service life of equipment.
The method of wastewater treatment and processing unit of desulfurization wastewater zero-emission of the present invention, desulfurization wastewater is through flocculation basin 1
After flocculation, precipitation, suspension, part Ca can remove2+、Mg2+, partial organic substances, the pollution factor such as COD, BOD, subsequently entering
Learn circulation granulating fluidized bed 2 and can remove most of Ca in desulfurization wastewater2+、Mg2+, to reduce the hardness of desulfurization wastewater, and obtain
Surface carries CaCO3With Mg (OH)2The bulky grain crystal seed of crystal is recycling；Desulfurization wastewater is after the activation of scale inhibiting cleaner 4 afterwards
Into nano filter membrance device 5, obtained strong brine can reuse again, remaining secondary water can then be used as chemicals production raw material, thus in
The zero-emission of desulfurization wastewater is truly realized, reduces the pollution to environment, has saved resource, had to resource
Effect utilizes, and whole processing procedure is green, non-secondary pollution.
Better embodiment of the present invention is the foregoing is only, but protection scope of the present invention is not limited thereto, it is any ripe
Know those skilled in the art the invention discloses technical scope in, the technique according to the invention design be subject to equivalent substitution or
Change the technical scheme of gained, should all be covered by protection scope of the present invention.
Claims (7)
1. a kind of method of wastewater treatment of desulfurization wastewater zero-emission, it is characterised in that comprise the following steps：
A, pre-process：Flocculation aid or flocculant are added into desulfurization wastewater, flocculation, sedimentation, collect supernatant after being well mixed；
B, softening is gone hard：Chemical agent and crystal seed are added into supernatant, makes the Ca in supernatant2+、Mg2+Ion forms CaCO3
With Mg (OH)2Crystal separates out, and reduces the hardness in supernatant；
C, film pre-treatment：Softening is gone using activation ceramics it is hard after waste water carry out activation process, realize scale removal to waste water, molten
Dirt, scale inhibition, the effect of sterilization；And activated delay ceramics make activated water maintain the state of activation；
D, film process：Desulfurization wastewater after step c processing is obtained into secondary water and strong brine through film process, strong brine is as benefit
Water-filling reuse, secondary water are used as chemicals production raw material.
2. the method for wastewater treatment of desulfurization wastewater zero-emission according to claim 1, it is characterised in that：Described in step b
Chemical agent is sodium hydroxide.
3. the method for wastewater treatment of desulfurization wastewater zero-emission according to claim 1, it is characterised in that：It is living described in step c
Change in ceramics and contain the one or more in lithium, rubidium, caesium, beryllium element；It is described activation delay ceramics in containing sodium, magnesium, phosphorus, iron,
The one or more of iodine, Zn-ef ficiency.
4. the method for wastewater treatment of desulfurization wastewater zero-emission according to claim 1, it is characterised in that：Film described in step d
Handle to carry out filtration treatment using NF membrane.
5. a kind of wastewater treatment equipment of desulfurization wastewater zero-emission, in method of wastewater treatment as claimed in claim 1, its
It is characterised by：The film process unit being connected including pretreatment unit, with pretreatment unit；
The pretreatment unit includes flocculation basin and the chemicrystallization being connected with flocculation basin circulation is granulating fluidized bed；The flocculation
The bottom in pond is provided with water inlet and sewage draining exit, and top is provided with purified liquor outlet, and water inlet is by the pipeline with the first water pump with taking off
Desulfurization wastewater output end in sulphur system is connected, purified liquor outlet with chemical cycle is granulating fluidized bed is connected；The chemical cycle is made
The bottom of grain fluid bed is sequentially provided with dosing mouth, crystal seed dispensing port and particulate emission mouth, and top exports provided with overflow；
The film process unit includes scale inhibiting cleaner and the reverse osmosis membrane apparatus being connected with scale inhibiting cleaner；The scale inhibition removes
Left chamber and right chamber room are divided into by plate inside dirty device, the plate has space, the left chamber with scale inhibiting cleaner bottom
Inwall be provided with nanometer antiscale cermet coating, the inwall of the right chamber room is provided with activation delay nano-ceramic layer, and in
Water inlet is set at the top of the left chamber, delivery port is set in the right chamber roof；The scale inhibiting cleaner water inlet is with changing
Learn to circulate granulating fluidized bed overflow and export and be connected, delivery port is connected with nano filter membrance device；The output end of the nano filter membrance device
Including divalent salts concentrate output end and monovalent salt penetrating fluid output end, divalent salts concentrate output end is connected with reuse tank, and one
Valency salt penetration liquid output end connection infiltration flow container.
6. the wastewater treatment equipment of desulfurization wastewater zero-emission according to claim 5, it is characterised in that：The chemical cycle
Cylinder is provided with granulating fluidized bed, there is interlayer, and the two of interlayer between the cylinder and the granulating fluidized bed inwall of chemical cycle
End opens.
7. the wastewater treatment equipment of desulfurization wastewater zero-emission according to claim 5, it is characterised in that：The flocculation basin enters
Pressure gauge and fluid flowmeter are set at the mouth of a river.
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| CN111547927A (en) * | 2020-05-15 | 2020-08-18 | 北京朗新明环保科技有限公司 | Induced crystallization heterogeneous nucleation device |
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