CN220845811U - Coking wastewater treatment system - Google Patents
Coking wastewater treatment system Download PDFInfo
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- CN220845811U CN220845811U CN202322486781.7U CN202322486781U CN220845811U CN 220845811 U CN220845811 U CN 220845811U CN 202322486781 U CN202322486781 U CN 202322486781U CN 220845811 U CN220845811 U CN 220845811U
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- catalytic oxidation
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- 238000004939 coking Methods 0.000 title claims abstract description 77
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 351
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 157
- 239000012528 membrane Substances 0.000 claims abstract description 120
- 230000003647 oxidation Effects 0.000 claims abstract description 119
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 119
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 81
- 150000003839 salts Chemical class 0.000 claims abstract description 72
- 238000004062 sedimentation Methods 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000011780 sodium chloride Substances 0.000 claims abstract description 41
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 27
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 26
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims description 56
- 239000002351 wastewater Substances 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 18
- 239000006096 absorbing agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 238000011033 desalting Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 230000015784 hyperosmotic salinity response Effects 0.000 claims 1
- 238000010612 desalination reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The utility model discloses a coking wastewater treatment system, which relates to the technical field of coking wastewater treatment and comprises a raw water pretreatment device, a raw water ozone contact oxidation device, a denitrification filter, a primary membrane concentrator, a concentrated water mixing sedimentation tank, a concentrated water ozone contact oxidation device, a secondary membrane concentrator, a membrane salt separator, a sodium sulfate crystallizer and a sodium chloride crystallizer which are sequentially communicated.
Description
Technical Field
The utility model relates to the technical field of coking wastewater treatment, in particular to a coking wastewater treatment system.
Background
The coking wastewater is industrial wastewater which is generated in the processes of coking, gas carbonization at high temperature, purification and byproduct recovery, contains volatile phenol, polycyclic aromatic hydrocarbon, oxygen, sulfur, nitrogen and other heterocyclic compounds, and is industrial organic wastewater which has high COD cr, high phenol value, high ammonia nitrogen and is difficult to treat.
At present, 80% of domestic coking plants generally adopt a coking wastewater treatment process flow taking traditional biological denitrification treatment as a core. The process section is divided into pretreatment, biochemical treatment and advanced treatment. Wherein, the pretreatment mainly adopts a physical and chemical method, such as an adsorption method, a coagulating sedimentation method, an ozone oxidation method and the like; the biochemical treatment process mainly comprises A/O, A 2/O and other processes; the main processes of the advanced treatment include a membrane process and an evaporation process, and the combination of the whole treatment process section can realize zero discharge treatment of coking wastewater.
However, because the TDS content in the coking wastewater is higher, when the salt content is more than or equal to 1%, the conventional A/O, A 2/O and other processes cannot realize stable operation of nitrogen removal, so that after salt separation by crystallization of an evaporator, the nitrate nitrogen content in the separated sodium chloride is higher, the quality of the separated sodium chloride is not up to the standard, and meanwhile, the mixed salt at the sodium chloride side is treated as hazardous waste, so that the treatment cost is higher.
Disclosure of utility model
The utility model aims to provide a coking wastewater treatment system, which solves the problems in the prior art, and is characterized in that nitrate nitrogen in coking wastewater is removed by inoculating salt-tolerant denitrifying bacteria in a denitrification filter, and the denitrification filter can continuously and stably run, so that high-efficiency denitrification is realized, the content of sodium sulfate and sodium chloride obtained by separation is ensured to be higher, the quality requirement is met, and the treatment cost of mixed salt is reduced.
In order to achieve the above object, the present utility model provides the following solutions:
the utility model provides a coking wastewater treatment system, which comprises a raw water pretreatment device, a raw water ozone contact oxidation device, a denitrification filter tank, a primary membrane concentrator, a concentrated water mixed sedimentation tank, a concentrated water ozone contact oxidation device, a secondary membrane concentrator and a membrane salt separator which are sequentially communicated, wherein a water inlet of the raw water pretreatment device is used for introducing coking wastewater, a precipitation reagent can be added into the raw water pretreatment device so as to reduce the hardness of the coking wastewater, the raw water ozone contact oxidation device can be used for introducing ozone so as to remove organic matters in the coking wastewater, the denitrification filter tank can be used for being inoculated by salt-tolerant denitrification bacteria so as to remove nitrate nitrogen in the coking wastewater, a first reverse osmosis membrane is arranged in the primary membrane concentrator, a concentrated water outlet of the primary membrane concentrator is communicated with a water inlet of the concentrated water mixed sedimentation tank so as to introduce the primary concentrated water into the concentrated water mixed sedimentation tank, the water can be introduced into the secondary membrane, the water is introduced into the secondary membrane concentrator so as to reduce the hardness of the secondary membrane, the water is introduced into the secondary membrane concentrator, the secondary membrane is used for being in contact with the water inlet of the concentrated membrane concentrator so as to form a second membrane, the concentrated water is concentrated and desalinated by the secondary membrane, the secondary membrane is used for being in contact with the concentrated and desalinated water, the secondary membrane is concentrated and desalinated by the secondary membrane, forming divalent salt concentrated water and monovalent salt water;
The sodium sulfate crystallizer is used for evaporating and crystallizing the divalent salt concentrated water to form a sodium sulfate product; the water outlet of the membrane salt separator is communicated with the water inlet of the sodium chloride crystallizer, so that the monovalent brine is introduced into the sodium chloride crystallizer, and the sodium chloride crystallizer is used for evaporating and crystallizing the monovalent brine to form a sodium chloride product.
Preferably, the raw water pretreatment device comprises a raw water tank, a raw water mixing sedimentation tank and an intermediate water tank which are sequentially communicated, wherein a water inlet of the raw water tank is used for introducing the coking wastewater, the raw water mixing sedimentation tank can be used for adding a sedimentation agent, and a water outlet of the intermediate water tank is communicated with a water inlet of the raw water ozone contact oxidation device.
Preferably, the raw water ozone contact oxidation device comprises a first ozone catalytic oxidation reactor and a first ozone generator, the water outlet of the intermediate water tank is communicated with the water inlet of the first ozone catalytic oxidation reactor, the ozone inlet of the first ozone catalytic oxidation reactor is connected with the first ozone generator, the first ozone generator is used for introducing ozone into the first ozone catalytic oxidation reactor so as to oxidize organic matters in the coking wastewater in the first ozone catalytic oxidation reactor to form carbon dioxide and water, and the water outlet of the first ozone catalytic oxidation reactor is communicated with the water inlet of the denitrification filter.
Preferably, the raw water ozone contact oxidation device further comprises a first tail gas absorber, a tail gas outlet is further formed in the first ozone catalytic oxidation reactor, the tail gas outlet of the first ozone catalytic oxidation reactor is connected with the first tail gas absorber, and the first tail gas absorber is used for absorbing carbon dioxide in the first ozone catalytic oxidation reactor.
Preferably, the water outlet of the raw water tank is communicated with the water inlet of the raw water mixing sedimentation tank through a first water pump; and the water outlet of the middle water tank is communicated with the water inlet of the first ozone catalytic oxidation reactor through a second water pump.
Preferably, the concentrated water ozone contact oxidation device comprises a second ozone catalytic oxidation reactor and a second ozone generator, a water outlet of the concentrated water mixing sedimentation tank is communicated with a water inlet of the second ozone catalytic oxidation reactor, an ozone inlet of the second ozone catalytic oxidation reactor is connected with the second ozone generator, and the second ozone generator is used for introducing ozone into the second ozone catalytic oxidation reactor so as to oxidize organic matters in the first-stage concentrated water in the second ozone catalytic oxidation reactor to form carbon dioxide and water, and a water outlet of the second ozone catalytic oxidation reactor is communicated with a water inlet of the second-stage membrane concentrator.
Preferably, the concentrated water ozone contact oxidation device further comprises a second tail gas absorber, a tail gas outlet is further formed in the second ozone catalytic oxidation reactor, the tail gas outlet of the second ozone catalytic oxidation reactor is connected with the second tail gas absorber, and the second tail gas absorber is used for absorbing carbon dioxide in the second ozone catalytic oxidation reactor.
Preferably, the water outlet of the denitrification filter is communicated with the water inlet of the primary membrane concentrator through a third water pump.
Compared with the prior art, the utility model has the following technical effects:
The utility model provides a coking wastewater treatment system, which comprises a raw water pretreatment device, a raw water ozone contact oxidation device, a denitrification filter tank, a primary membrane concentrator, a concentrated water mixing sedimentation tank, a concentrated water ozone contact oxidation device, a secondary membrane concentrator, a membrane salt separator, a sodium sulfate crystallizer and a sodium chloride crystallizer, wherein when wastewater treatment is carried out, coking wastewater firstly enters the raw material pretreatment device, a sedimentation reagent is added to reduce the hardness of the coking wastewater, then enters the raw water ozone contact oxidation device, organic matters in the coking wastewater are removed through ozone contact oxidation, then enters the denitrification filter tank, nitrate nitrogen in the coking wastewater is removed through inoculating salt-tolerant denitrifying bacteria in the denitrification filter tank, the denitrification filter tank can continuously and stably run to realize high-efficiency denitrification, then the coking wastewater enters the primary membrane concentrator for concentration and desalination, forming first-stage concentrated water and first-stage desalted water, wherein the first-stage concentrated water enters a concentrated water mixing sedimentation tank, a sedimentation reagent is added to reduce the hardness of the first-stage concentrated water, the first-stage concentrated water enters a concentrated water ozone contact oxidation device, organic matters in the first-stage concentrated water are removed through ozone contact oxidation, then the first-stage concentrated water enters a second-stage membrane concentrator for concentration desalination to form second-stage concentrated water and second-stage desalted water, the second-stage concentrated water enters a membrane salt separator for concentration desalination to divalent salt in the second-stage concentrated water to form divalent salt concentrated water and monovalent salt water, the divalent salt concentrated water and the monovalent salt water respectively enter a sodium sulfate crystallizer and a sodium chloride crystallizer for evaporation crystallization, the content of sodium sulfate and sodium chloride obtained by separation is guaranteed to be higher, the quality requirements are met, and the treatment cost of mixed salt is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present utility model or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present utility model, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a coking wastewater treatment system provided by an embodiment of the present utility model;
Fig. 2 is a schematic workflow diagram of a coking wastewater treatment system according to an embodiment of the present utility model.
In the figure: 1-raw water tank, 2-raw water mixing sedimentation tank, 3-middle water tank, 4-raw water ozone contact oxidation device, 5-denitrification filter tank, 6-first-stage membrane concentrator, 7-concentrated water mixing sedimentation tank, 8-concentrated water ozone contact oxidation device, 9-second-stage membrane concentrator, 10-membrane salt separator, 11-sodium sulfate crystallizer, and 12-sodium chloride crystallizer.
Detailed Description
The following description of the embodiments of the present utility model will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present utility model, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model.
The utility model aims to provide a coking wastewater treatment system, which solves the problems in the prior art, and is characterized in that nitrate nitrogen in coking wastewater is removed by inoculating salt-tolerant denitrifying bacteria in a denitrification filter, and the denitrification filter can continuously and stably run, so that high-efficiency denitrification is realized, the content of sodium sulfate and sodium chloride obtained by separation is ensured to be higher, the quality requirement is met, and the impurity salt treatment cost is reduced.
In order that the above-recited objects, features and advantages of the present utility model will become more readily apparent, a more particular description of the utility model will be rendered by reference to the appended drawings and appended detailed description.
As shown in fig. 1-2, the present embodiment provides a coking wastewater treatment system, which comprises a raw water tank 1, a raw water mixing sedimentation tank 2, a middle water tank 3, a raw water ozone contact oxidation device 4, a denitrification filter 5, a primary membrane concentrator 6, a concentrated water mixing sedimentation tank 7, a concentrated water ozone contact oxidation device 8, a secondary membrane concentrator 9 and a membrane salt separator 10 which are sequentially communicated.
In the embodiment, the water inlet of the raw water tank 1 is used for introducing coking wastewater, the raw water tank 1 calculates the volume according to the residence time of 1h-2h, so that the sufficient buffer capacity of the incoming water can be ensured, and meanwhile, the condition that the system cannot stably run due to fluctuation of the water quality index of the incoming water can be avoided, and the functions of balancing the water quantity and the water quality are realized; the water outlet of the raw water tank 1 is communicated with the water inlet of the raw water mixing sedimentation tank 2 through a first water pump, the raw water mixing sedimentation tank 2 can be used for adding a sedimentation agent to reduce the hardness of coking wastewater, and the raw water mixing sedimentation tank 2 is required to be provided with the raw water mixing sedimentation tank 2, wherein the coking wastewater has higher hardness mainly because of the existence of calcium and magnesium, if the coking wastewater with higher hardness directly enters a membrane concentration unit, scale is extremely easy to generate to cause the blockage of membrane holes, so that the membrane produced water is reduced, the scale with the hardness is complicated in components, the scale cannot be thoroughly cleaned by washing with water, corresponding acid washing is required to be adopted, the operation agent cost of the membrane concentration unit is increased, and meanwhile, the frequent acid washing also can lead to the loss of membrane materials to seriously reduce the service life of membranes, so that the raw water mixing sedimentation tank 2 is arranged in the system, and the hardness of the coking wastewater is reduced by adding sedimentation agents such as lime, soda, PFS, PAM and the like, and the removal rate of the hardness is 65% -70%; as a possible example, the PFS dosage is 20ppm to 30ppm and the PAM dosage is 1ppm to 3ppm.
In this embodiment, the raw water ozone contact oxidation device 4 can supply ozone to remove organic matters in the coking wastewater, and it should be noted that the coking wastewater has higher COD cr,CODcr, mainly organic matters which are difficult to degrade, and is very easy to cause organic matter pollution of the membrane in the membrane concentration unit, and meanwhile, the whiteness, purity and other qualities of the final evaporated crystal salt are also affected, so that the membrane concentration unit and the evaporated crystal unit are frequently cleaned, and the safe and stable operation of the system is affected.
In this embodiment, the denitrification filter 5 can be inoculated by salt-tolerant denitrifying bacteria, in the denitrification filter 5, the salt-tolerant denitrifying bacteria and nitrate nitrogen in the coking wastewater are subjected to denitrification reaction to remove the nitrate nitrogen in the coking wastewater, the removal rate of the nitrate nitrogen is not less than 80% -90%, it is required to say that the content of nitrate nitrogen in the coking wastewater is higher, if the sodium chloride obtained by separation is higher after crystallization and salt separation, the quality is not up to standard, and the mixed salt at the sodium chloride side is used as hazardous waste treatment, the disposal cost is higher, so that most of nitrate in the coking wastewater needs to be removed before crystallization and salt separation of the coking wastewater; according to the system, the denitrifying filter 5 is inoculated with the salt-tolerant denitrifying bacteria to remove nitrate nitrogen in the coking wastewater, and the denitrifying filter 5 can continuously and stably run, so that the problem that the sodium nitrate and sodium chloride cannot be separated in the sodium chloride side of the existing sewage treatment facility of the coking wastewater, so that the disposal cost of mixed salt on the sodium chloride side is high is solved, and meanwhile, the system can be suitable for denitrification under the condition of high TDS wastewater; the system is not only suitable for treating coking wastewater, but also suitable for treating high-salt wastewater (wastewater with salt content more than 1 percent), and has wide application range.
In the embodiment, the water outlet of the denitrification filter 5 is communicated with the water inlet of the primary membrane concentrator 6 through a third water pump, a first reverse osmosis membrane is arranged in the primary membrane concentrator 6 and is used for concentrating and desalting coking wastewater, the desalination rate is more than or equal to 97%, primary concentrated water and primary desalted water are formed, wherein the primary concentrated water is discharged from the concentrated water outlet of the primary membrane concentrator 6, and the primary desalted water is discharged from the water outlet of the primary membrane concentrator 6 and can be directly used as reuse water; the concentrated water outlet of the first-stage membrane concentrator 6 is communicated with the water inlet of the concentrated water mixing sedimentation tank 7 so as to introduce the first-stage concentrated water into the concentrated water mixing sedimentation tank 7, the concentrated water mixing sedimentation tank 7 can be used for adding a sedimentation agent so as to reduce the hardness of the first-stage concentrated water, and the concentrated water ozone contact oxidation device 8 can be used for introducing ozone so as to remove organic matters in the first-stage concentrated water; it should be noted that, the first-stage concentrated water produced by the first-stage membrane concentrator 6 has higher hardness and COD cr, so that the system is provided with the concentrated water mixing sedimentation tank 7 and the concentrated water ozone contact oxidation device 8, the hardness of the first-stage concentrated water is reduced by adding lime, soda ash, PFS, PAM and other medicaments in the concentrated water mixing sedimentation tank 7, the removal rate of the hardness is 65% -70%, the organic matters in the first-stage concentrated water are removed by introducing ozone into the concentrated water ozone contact oxidation device 8, the removal rate of the COD cr is 50% -55%, and the continuous and stable operation of the subsequent device is ensured.
In the embodiment, a second reverse osmosis membrane is arranged in the second-stage membrane concentrator 9 and is used for concentrating and desalting the first-stage concentrated water, wherein the desalination rate is more than or equal to 97%, and the second-stage concentrated water and second-stage desalted water are formed, and the second-stage concentrated water is discharged from a concentrated water outlet of the second-stage membrane concentrator 9; the concentrated water outlet of the second-stage membrane concentrator 9 is communicated with the water inlet of the membrane salt separator 10 to introduce the second-stage concentrated water into the membrane salt separator 10, a nanofiltration membrane is arranged in the membrane salt separator 10, the nanofiltration membrane is used for concentrating and desalting divalent salt in the second-stage concentrated water, the desalination rate is more than or equal to 97%, divalent salt concentrated water and monovalent salt water are formed, namely, the monovalent ions are separated from the divalent ions by utilizing the salt separation characteristic of the nanofiltration membrane, the purpose of salt separation is achieved, the formed divalent salt concentrated water is led out from the concentrated water outlet of the membrane salt separator 10, and the formed monovalent salt water is led out from the water outlet of the membrane salt separator 10; the system also comprises a sodium sulfate crystallizer 11 and a sodium chloride crystallizer 12, wherein the concentrated water outlet of the membrane salt separator 10 is communicated with the water inlet of the sodium sulfate crystallizer 11 so as to introduce the divalent salt concentrated water into the sodium sulfate crystallizer 11, the sodium sulfate crystallizer 11 is used for evaporating and crystallizing the divalent salt concentrated water to form a sodium sulfate product, and the sodium sulfate content is more than or equal to 97 percent, so that the quality requirement is met; the water outlet of the membrane salt separator 10 is communicated with the water inlet of the sodium chloride crystallizer 12 so as to introduce monovalent brine into the sodium chloride crystallizer 12, and the sodium chloride crystallizer 12 is used for evaporating and crystallizing the monovalent brine to form a sodium chloride product, wherein the sodium chloride content is more than or equal to 98.5%, the quality requirement is met, and the treatment cost of mixed salt is reduced.
In this embodiment, the raw water ozone contact oxidation device 4 includes a first ozone catalytic oxidation reactor and a first ozone generator, the water outlet of the intermediate water tank 3 is communicated with the water inlet of the first ozone catalytic oxidation reactor through a second water pump, the ozone inlet of the first ozone catalytic oxidation reactor is connected with the first ozone generator, the first ozone generator is used for introducing ozone into the first ozone catalytic oxidation reactor so as to oxidize organic matters in coking wastewater in the first ozone catalytic oxidation reactor to form carbon dioxide and water, and the water outlet of the first ozone catalytic oxidation reactor is communicated with the water inlet of the denitrification filter 5.
Further, the raw water ozone contact oxidation device 4 further comprises a first tail gas absorber, a tail gas outlet is further formed in the first ozone catalytic oxidation reactor, the tail gas outlet of the first ozone catalytic oxidation reactor is connected with the first tail gas absorber, and the first tail gas absorber is used for absorbing carbon dioxide in the first ozone catalytic oxidation reactor, reducing carbon dioxide emission and protecting the environment.
In this embodiment, the concentrated water ozone contact oxidation device 8 includes a second ozone catalytic oxidation reactor and a second ozone generator, the water outlet of the concentrated water mixing sedimentation tank 7 is communicated with the water inlet of the second ozone catalytic oxidation reactor, the ozone inlet of the second ozone catalytic oxidation reactor is connected with the second ozone generator, the second ozone generator is used for introducing ozone into the second ozone catalytic oxidation reactor to oxidize organic matters in the first-stage concentrated water in the second ozone catalytic oxidation reactor to form carbon dioxide and water, and the water outlet of the second ozone catalytic oxidation reactor is communicated with the water inlet of the second-stage membrane concentrator 9.
Further, the concentrated water ozone contact oxidation device 8 further comprises a second tail gas absorber, a tail gas outlet is further formed in the second ozone catalytic oxidation reactor, the tail gas outlet of the second ozone catalytic oxidation reactor is connected with the second tail gas absorber, and the second tail gas absorber is used for absorbing carbon dioxide in the second ozone catalytic oxidation reactor, reducing carbon dioxide emission and protecting the environment.
As a possible example, the system further comprises an automatic monitoring system, wherein the automatic monitoring system utilizes various detection instruments to measure, indicate or record main process parameters, and mainly comprises various medicament dosage monitoring, pH monitoring, ORP monitoring, conductivity monitoring, pressure monitoring, water inlet and outlet flow monitoring of various devices and the like; specifically, the PLC can be used for monitoring the operation parameters of the equipment in real time, and once the system finds out abnormal operation, an alarm signal can be sent out in time.
Application example 1
(1) Raw water tank 1: the coking wastewater firstly enters a raw water tank 1, the water quality and the water quantity are balanced through the raw water tank 1, and then the coking wastewater is pumped into a raw water mixing sedimentation tank 2 through a first water pump; the quality of the coking wastewater in the raw water tank 1 is as follows: NO 3 - mg/L (converted nitrate nitrogen 220.16 mg/L), TDS 12236.60mg/L, total hardness (calculated as CaCO 3) 781mg/L, COD Cr 654mg/L, total alkalinity (calculated as CaCO 3) 901mg/L, and treated water volume 100m 3/h.
(2) Raw water mixing sedimentation tank 2: adding a precipitation reagent into the raw water mixing and precipitation tank 2 to reduce the hardness of the coking wastewater; the dosage of the precipitation medicament is as follows: the dosage of lime is 485ppm, the dosage of sodium carbonate is 438ppm, the dosage of PFS is 20ppm and the dosage of PAM is 1ppm; the hardness of the effluent of the raw water mixing sedimentation tank 2 is 234.3mg/L, and the hardness removal rate is 70%.
(3) Intermediate water tank 3: the effluent of the raw water mixing sedimentation tank 2 enters the middle water tank 3 for buffering, and is pumped into the raw water ozone contact oxidation device 4 through the second water pump.
(4) Raw water ozone contact oxidation device 4: in the raw water ozone contact oxidation device 4, removing organic matters in the coking wastewater through ozone contact oxidation; the dosage of ozone in the raw water ozone contact oxidation device 4 is 65.4Kg, the COD cr of the effluent of the raw water ozone contact oxidation device 4 is 327mg/L, and the removal rate of COD cr is 50%.
(5) Denitrification filter 5: the effluent of the raw water ozone contact oxidation device 4 enters the denitrification filter 5 to carry out denitrification reaction, the removal rate of the nitrate nitrogen is 80 percent, and the nitrate nitrogen in the effluent of the denitrification filter 5 is 44mg/L.
(6) Primary membrane concentrator 6: the effluent of the denitrification filter 5 is pumped into a first-stage membrane concentrator 6 by a third water pump to be concentrated and desalted, and the produced water can be directly recycled, and the desalination rate is 97%; the TDS of the water producing end of the primary membrane concentrator 6 is 367mg/L, the recovery rate is 70%, the hardness of the concentrated water end of the primary membrane concentrator 6 is 781mg/L, the COD is 1090mg/L, and the TDS is 40788mg/L.
(7) Concentrated water mixing sedimentation tank 7: the first-stage concentrated water of the first-stage membrane concentrator 6 enters a concentrated water mixing sedimentation tank 7, and a sedimentation agent is added into the concentrated water mixing sedimentation tank 7 to reduce the hardness of the first-stage concentrated water; the hardness of the inlet water of the concentrated water mixed sedimentation tank 7 is 781mg/L, the hardness of the outlet water of the concentrated water mixed sedimentation tank 7 is 234.3mg/L, and the hardness removal rate is 70%.
(8) Concentrated water ozone contact oxidation device 8: the effluent of the concentrated water mixing sedimentation tank 7 enters a concentrated water ozone contact oxidation device 8, and organic matters in the first-stage concentrated water are removed through ozone contact oxidation in the concentrated water ozone contact oxidation device 8; the effluent COD cr of the concentrated water ozone contact oxidation device 8 is 545mg/L, and the removal rate of COD cr is 50%.
(9) Secondary membrane concentrator 9: the effluent of the concentrated water ozone contact oxidation device 8 enters a secondary membrane concentrator 9 for concentration and desalination, the desalination rate is 97%, the recovery rate is 60%, and the TDS of the concentrated water end of the secondary membrane concentrator 9 is 101970mg/L.
(10) Membrane salt separator 10: the second-stage concentrated water of the second-stage membrane concentrator 9 enters the membrane salt separator 10, the membrane salt separator 10 carries out concentration desalination on divalent salt in the second-stage concentrated water, the desalination rate is 97%, the recovery rate is 50%, the TDS of the water producing end of the membrane salt separator 10 is 45886.5mg/L, and the TDS of the concentrated water end of the membrane salt separator 10 is 131541mg/L.
(11) Sodium sulfate crystallizer 11: the divalent salt concentrated water of the membrane salt separator 10 enters a sodium sulfate crystallizer 11 for evaporation and crystallization to form sodium sulfate products, wherein the sodium sulfate content is 97%, and the quality requirements are met.
(12) Sodium chloride crystallizer 12: the monovalent salt water of the membrane salt separator 10 enters the sodium chloride crystallizer 12 for evaporation and crystallization to form sodium chloride products, wherein the sodium chloride content is 98.5 percent, and the quality requirements are met.
Application example two
(1) Raw water tank 1: the coking wastewater firstly enters a raw water tank 1, the water quality and the water quantity are balanced through the raw water tank 1, and then the coking wastewater is pumped into a raw water mixing sedimentation tank 2 through a first water pump; the quality of the coking wastewater in the raw water tank 1 is as follows: NO 3 - is 850mg/L (converted into nitrate nitrogen 192 mg/L), TDS is 10000mg/L, total hardness (calculated as CaCO 3) is 750mg/L, COD Cr is 600mg/L, total alkalinity (calculated as CaCO 3) is 800mg/L, and the treated water amount is 100m 3/h.
(2) Raw water mixing sedimentation tank 2: adding a precipitation reagent into the raw water mixing and precipitation tank 2 to reduce the hardness of the coking wastewater; the dosage of the precipitation medicament is as follows: lime dosage is 432ppm, sodium carbonate dosage is 488ppm, PFS dosage is 20ppm and PAM dosage is 1ppm; the hardness of the effluent of the raw water mixing sedimentation tank 2 is 225mg/L, and the hardness removal rate is 70%.
(3) Intermediate water tank 3: the effluent of the raw water mixing sedimentation tank 2 enters the middle water tank 3 for buffering, and is pumped into the raw water ozone contact oxidation device 4 through the second water pump.
(4) Raw water ozone contact oxidation device 4: in the raw water ozone contact oxidation device 4, removing organic matters in the coking wastewater through ozone contact oxidation; the dosage of ozone in the raw water ozone contact oxidation device 4 is 60Kg, the effluent COD cr of the raw water ozone contact oxidation device 4 is 300mg/L, and the removal rate of COD cr is 50%.
(5) Denitrification filter 5: the effluent of the raw water ozone contact oxidation device 4 enters the denitrification filter 5 to carry out denitrification reaction, the removal rate of the nitrate nitrogen is 80 percent, and the nitrate nitrogen in the effluent of the denitrification filter 5 is 38.4mg/L.
(6) Primary membrane concentrator 6: the effluent of the denitrification filter 5 is pumped into a first-stage membrane concentrator 6 by a third water pump to be concentrated and desalted, and the produced water can be directly recycled, and the desalination rate is 97%; the water producing end TDS of the primary membrane concentrator 6 is 300mg/L, the recovery rate is 70%, the hardness of the concentrated water end of the primary membrane concentrator 6 is 750mg/L, the COD is 1000mg/L, and the TDS is 33300mg/L.
(7) Concentrated water mixing sedimentation tank 7: the first-stage concentrated water of the first-stage membrane concentrator 6 enters a concentrated water mixing sedimentation tank 7, and a sedimentation agent is added into the concentrated water mixing sedimentation tank 7 to reduce the hardness of the first-stage concentrated water; the hardness of the inlet water of the concentrated water mixed sedimentation tank 7 is 750mg/L, the hardness of the outlet water of the concentrated water mixed sedimentation tank 7 is 225mg/L, and the hardness removal rate is 70%.
(8) Concentrated water ozone contact oxidation device 8: the effluent of the concentrated water mixing sedimentation tank 7 enters a concentrated water ozone contact oxidation device 8, and organic matters in the first-stage concentrated water are removed through ozone contact oxidation in the concentrated water ozone contact oxidation device 8; the COD cr of the effluent of the concentrated water ozone contact oxidation device 8 is 500mg/L, and the removal rate of COD cr is 50%.
(9) Secondary membrane concentrator 9: the effluent of the concentrated water ozone contact oxidation device 8 enters a secondary membrane concentrator 9 for concentration and desalination, the desalination rate is 97%, the recovery rate is 60%, and the TDS of the concentrated water end of the secondary membrane concentrator 9 is 83250mg/L.
(10) Membrane salt separator 10: the second-stage concentrated water of the second-stage membrane concentrator 9 enters the membrane salt separator 10, the membrane salt separator 10 carries out concentration desalination on divalent salt in the second-stage concentrated water, the desalination rate is 97%, the recovery rate is 50%, the TDS of the water producing end of the membrane salt separator 10 is 37462mg/L, and the TDS of the concentrated water end of the membrane salt separator 10 is 108331mg/L.
(11) Sodium sulfate crystallizer 11: the divalent salt concentrated water of the membrane salt separator 10 enters a sodium sulfate crystallizer 11 for evaporation and crystallization to form sodium sulfate products, wherein the sodium sulfate content is 97%, and the quality requirements are met.
(12) Sodium chloride crystallizer 12: the monovalent salt water of the membrane salt separator 10 enters the sodium chloride crystallizer 12 for evaporation and crystallization to form sodium chloride products, wherein the sodium chloride content is 98.5 percent, and the quality requirements are met.
In summary, according to the coking wastewater treatment system provided by the embodiment, the denitrifying filter tank 5 is inoculated with the salt-tolerant denitrifying bacteria, so that the removal rate of nitrate nitrogen in coking wastewater can reach 80% -90%, the content of sodium sulfate and sodium chloride obtained by separation is high, and the quality requirement is met.
By way of illustration of application example one, the sodium chloride first grade product isolated in application example one has 758kg/d, if calculated according to the current recovery price of 300 yuan/ton, the benefit that can be produced for the user is 227.4 yuan/d; if the sodium nitrate content in the separated sodium chloride product is higher and the quality is not up to standard, the sodium nitrate is treated as the mixed salt, then the user needs to outsource 1900kg/d mixed salt, and if the cost is calculated according to 3000 yuan/ton of recovery price, the cost for recovering the mixed salt is 5700 yuan/d for the user. Therefore, it is necessary to denitrify the coking wastewater to meet the quality requirements of the sodium sulfate and sodium chloride content in the final product.
The principles and embodiments of the present utility model have been described in detail with reference to specific examples, which are provided to facilitate understanding of the method and core ideas of the present utility model; also, it is within the scope of the present utility model to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the utility model.
Claims (8)
1. A coking wastewater treatment system, characterized in that: the method comprises a raw water pretreatment device, a raw water ozone contact oxidation device, a denitrification filter tank, a primary membrane concentrator, a concentrated water mixed sedimentation tank, a concentrated water ozone contact oxidation device, a secondary membrane concentrator and a membrane salt separator which are sequentially communicated, wherein a water inlet of the raw water pretreatment device is used for introducing coking wastewater, the raw water pretreatment device can be used for adding a sedimentation reagent to reduce the hardness of the coking wastewater, the raw water ozone contact oxidation device can be used for introducing ozone to remove organic matters in the coking wastewater, the denitrification filter tank can be used for inoculating salt tolerance bacteria to remove nitrate nitrogen in the coking wastewater, a first reverse osmosis membrane is arranged in the primary membrane concentrator, a concentrated water outlet of the primary membrane concentrator is communicated with a water inlet of the concentrated water mixed sedimentation tank to introduce the primary concentrated water into the mixed sedimentation tank, the concentrated water mixed sedimentation tank can be used for introducing ozone to remove the organic matters in the coking wastewater, a divalent concentration water inlet of the secondary membrane is used for introducing the divalent concentration water into the secondary membrane, a second membrane is arranged in the primary membrane concentrator to form a second membrane, the divalent concentration water inlet of the secondary membrane is used for desalting membrane, the divalent concentration water is used for introducing the divalent concentration water into the secondary membrane to form a second membrane concentrator, the divalent concentration water is used for desalting membrane is used for concentrating and the second membrane, the divalent concentration water is introduced into the second membrane concentrator, forming divalent salt concentrated water and monovalent salt water;
The sodium sulfate crystallizer is used for evaporating and crystallizing the divalent salt concentrated water to form a sodium sulfate product; the water outlet of the membrane salt separator is communicated with the water inlet of the sodium chloride crystallizer, so that the monovalent brine is introduced into the sodium chloride crystallizer, and the sodium chloride crystallizer is used for evaporating and crystallizing the monovalent brine to form a sodium chloride product.
2. The coking wastewater treatment system according to claim 1, wherein: the raw water pretreatment device comprises a raw water tank, a raw water mixing sedimentation tank and an intermediate water tank which are sequentially communicated, wherein a water inlet of the raw water tank is used for introducing coking wastewater, the raw water mixing sedimentation tank can be used for adding a sedimentation agent, and a water outlet of the intermediate water tank is communicated with a water inlet of the raw water ozone contact oxidation device.
3. The coking wastewater treatment system according to claim 2, wherein: the raw water ozone contact oxidation device comprises a first ozone catalytic oxidation reactor and a first ozone generator, wherein a water outlet of the intermediate water tank is communicated with a water inlet of the first ozone catalytic oxidation reactor, an ozone inlet of the first ozone catalytic oxidation reactor is connected with the first ozone generator, and the first ozone generator is used for introducing ozone into the first ozone catalytic oxidation reactor so as to oxidize organic matters in coking wastewater in the first ozone catalytic oxidation reactor to form carbon dioxide and water, and a water outlet of the first ozone catalytic oxidation reactor is communicated with a water inlet of the denitrification filter.
4. A coking wastewater treatment system according to claim 3 in which: the raw water ozone contact oxidation device further comprises a first tail gas absorber, a tail gas outlet is further formed in the first ozone catalytic oxidation reactor, the tail gas outlet of the first ozone catalytic oxidation reactor is connected with the first tail gas absorber, and the first tail gas absorber is used for absorbing carbon dioxide in the first ozone catalytic oxidation reactor.
5. A coking wastewater treatment system according to claim 3 in which: the water outlet of the raw water tank is communicated with the water inlet of the raw water mixing sedimentation tank through a first water pump; and the water outlet of the middle water tank is communicated with the water inlet of the first ozone catalytic oxidation reactor through a second water pump.
6. The coking wastewater treatment system according to claim 1, wherein: the concentrated water ozone contact oxidation device comprises a second ozone catalytic oxidation reactor and a second ozone generator, a water outlet of the concentrated water mixing sedimentation tank is communicated with a water inlet of the second ozone catalytic oxidation reactor, an ozone inlet of the second ozone catalytic oxidation reactor is connected with the second ozone generator, and the second ozone generator is used for introducing ozone into the second ozone catalytic oxidation reactor so as to oxidize organic matters in the first-stage concentrated water in the second ozone catalytic oxidation reactor to form carbon dioxide and water, and a water outlet of the second ozone catalytic oxidation reactor is communicated with a water inlet of the second-stage membrane concentrator.
7. The coking wastewater treatment system according to claim 6, wherein: the concentrated water ozone contact oxidation device further comprises a second tail gas absorber, a tail gas outlet is further formed in the second ozone catalytic oxidation reactor, the tail gas outlet of the second ozone catalytic oxidation reactor is connected with the second tail gas absorber, and the second tail gas absorber is used for absorbing carbon dioxide in the second ozone catalytic oxidation reactor.
8. The coking wastewater treatment system according to claim 1, wherein: and the water outlet of the denitrification filter is communicated with the water inlet of the primary membrane concentrator through a third water pump.
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