CN111517528A - Device and method for treating ammonia nitrogen in desulfurization wastewater by membrane absorption method - Google Patents
Device and method for treating ammonia nitrogen in desulfurization wastewater by membrane absorption method Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 116
- 239000012528 membrane Substances 0.000 title claims abstract description 108
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 91
- 230000023556 desulfurization Effects 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 56
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005352 clarification Methods 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 16
- 238000005189 flocculation Methods 0.000 claims abstract description 7
- 230000016615 flocculation Effects 0.000 claims abstract description 6
- 239000003814 drug Substances 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 24
- 239000010802 sludge Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 239000013049 sediment Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052567 struvite Inorganic materials 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 230000009615 deamination Effects 0.000 description 3
- 238000006481 deamination reaction Methods 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 235000013372 meat Nutrition 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a device and a method for treating ammonia nitrogen in desulfurization wastewater by a membrane absorption method, wherein the device comprises the following components: an alkaline agent adding device is arranged at the top end of the alkali adjusting tank; an organic sulfur feeding device is arranged at the top end of the heavy removal tank, the inlet end of the heavy removal tank is connected with the outlet end of the alkali adjusting tank, and the outlet end of the heavy removal tank is connected with the inlet end of the clarification tank; the inlet end of the middle water tank is connected with the outlet end of the clarification tank, and the outlet end of the middle water tank is connected with the first inlet end of the membrane absorption assembly; the inlet end of the absorption liquid pool is connected with the first outlet end of the membrane absorption assembly, and the outlet end of the absorption liquid pool is connected with the second inlet end of the membrane absorption assembly. The method comprises the following steps: adding an alkaline medicament to adjust the pH value of the desulfurization wastewater to 11-13; organic sulfur is added to remove heavy metals in the desulfurization wastewater; removing suspended matters in the desulfurization wastewater through flocculation and clarification; the supernatant enters an intermediate water tank; separating ammonia nitrogen in the desulfurization wastewater through a separation membrane and absorbing the ammonia nitrogen by absorption liquid to remove the ammonia nitrogen.
Description
Technical Field
The invention relates to the technical field of desulfurization wastewater treatment, in particular to a device and a method for treating ammonia nitrogen in desulfurization wastewater by using a membrane absorption method.
Background
With the continuous improvement of the environmental protection requirement in China, the limestone-gypsum wet desulphurization technology has the advantages of high desulphurization efficiency, stable operation and the like, and is widely applied to flue gas desulphurization in the fields of coal-fired power plants, steel plants and the like. In the limestone-gypsum wet desulphurization process, in order to ensure the quality of gypsum, the desulphurization efficiency and the like, a certain amount of desulphurization slurry needs to be discharged, and finally desulphurization wastewater is generated. The desulfurization wastewater has complex components and contains high-concentration suspended matters, ammonia nitrogen, sulfate, calcium and magnesium ions, chloride ions and various heavy metals. The denitration process is applied in a large scale, the condition of excessive ammonia spraying is common, and the ammonia nitrogen in the wastewater is greatly improved to 5000 mg/L. At present, desulfurization wastewater is mainly treated by a triple box process, suspended matters and heavy metals in the wastewater are mainly removed, and ammonia nitrogen is not obviously removed, so that the ammonia nitrogen exceeds the standard seriously.
The high ammonia wastewater has wide sources in actual production, such as industries of coking, petrochemical industry, drug production, cultivation, chemical fertilizer, meat processing and the like, garbage penetrating fluid, animal excrement and the like. For the treatment of wastewater containing high-concentration ammonia nitrogen, a better removal effect is difficult to obtain by directly adopting a biological method for treatment. In addition, ammonia is used as an important chemical raw material, ammonia nitrogen in high ammonia wastewater is converted into nitrogen through biological treatment and is discharged into the atmosphere, resource waste is also realized, and the circular economy concept is not met. Therefore, the actual high-ammonia wastewater is mostly pretreated by a physicochemical method and then subjected to subsequent biological treatment according to the actual situation. The currently common treatment method of high-concentration ammonia nitrogen wastewater mainly comprises a chemical precipitation method and a stripping method.
The chemical precipitation method mainly refers to a Magnesium Ammonium Phosphate (MAP) method, and the method utilizes the water-insoluble property of Magnesium Ammonium Phosphate to add PO-containing wastewater4 3+And Mg2+Chemical agent of ion, NH in wastewater4 +And PO4 3+And Mg2+The ion reaction generates magnesium ammonium phosphate sediment, and finally ammonia in the wastewater is removed. The chemical precipitation method has more defects, mainly including large production amount of precipitated sludge and serious secondary pollution; the dosage of the precipitation medicament is large, and the medicament cost is high.
The stripping method is that the waste water is treated under the alkaline condition (generally, the pH value is adjusted to about 11.0), then air or steam is introduced into the waste water, free molecular ammonia overflows from the waste water under the stirring and entrainment action of the air, and then the overflowing mixed gas is absorbed by acid liquor, so that the ammonia in the waste water is removed and the ammonia is recovered in the form of ammonium salt. When high-concentration ammonia nitrogen in the wastewater is treated, the stripping method has the advantages of high efficiency, strong adaptability to water quality change and capability of recovering ammonia in the wastewater. However, the stripping method has many disadvantages, for example, when pressurized air is used for stripping at normal temperature, the ammonia nitrogen removal effect is poor, and the air demand is large; when steam stripping is adopted, the energy consumption is high, and the volume of the waste water is obviously increased due to the condensation effect of the steam; in addition, the blow-off method also has the problems of easy scaling of equipment and inconvenient operation and maintenance of the device.
In order to avoid the standard emission of ammonia nitrogen in the desulfurization wastewater and the recovery of ammonia nitrogen resources, the development of a novel desulfurization wastewater treatment method is an urgent problem in view of the defects and shortcomings of the existing desulfurization wastewater concentration process.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a device and a method for treating ammonia nitrogen in desulfurization wastewater by using a membrane absorption method.
The invention provides a device for treating ammonia nitrogen in desulfurization wastewater by a membrane absorption method, which comprises the following steps:
the top end of the alkali adjusting tank is provided with an alkaline agent adding device;
the top end of the heavy component removal tank is provided with an organic sulfur feeding device, the inlet end of the heavy component removal tank is connected with the outlet end of the alkali adjusting tank, and the outlet end of the heavy component removal tank is connected with the inlet end of the clarification tank;
the inlet end of the middle water tank is connected with the outlet end of the clarification tank, the outlet end of the middle water tank is connected with the first inlet end of the membrane absorption assembly, and a separation membrane is arranged in the membrane absorption assembly;
and the inlet end of the absorption liquid pool is connected with the first outlet end of the membrane absorption assembly, the outlet end of the absorption liquid pool is connected with the second inlet end of the membrane absorption assembly, and the first inlet end and the second inlet end of the membrane absorption assembly are respectively arranged on two sides of the separation membrane. .
As a further improvement of the invention, a first stirring device is arranged in the alkali adjusting tank, a second stirring device is arranged in the weight removing tank, and a third stirring device is arranged in the absorption liquid tank.
As a further improvement of the invention, the bottom end of the clarification tank is connected with the inlet end of a sludge dewatering machine, and the outlet end of the sludge dewatering machine is connected with the inlet end of the alkali adjusting tank.
As a further improvement of the invention, a first water pump is arranged between the outlet end of the middle water tank and the first inlet end of the membrane absorption assembly; and a second water pump is arranged between the outlet end of the absorption liquid pool and the second inlet end of the membrane absorption assembly.
As a further improvement of the invention, a waste liquid output pipeline is arranged at the second outlet end of the membrane absorption assembly, and an acid adding device is arranged on the waste liquid output pipeline.
As a further improvement of the invention, a multi-media filter is arranged between the outlet end of the clarification tank and the inlet end of the middle water tank.
As a further improvement of the invention, the separation membrane is a hydrophobic membrane, and the separation membrane is one or more of a flat plate type, a hollow fiber type and a roll type.
The invention also provides a method for treating ammonia nitrogen in desulfurization wastewater by using a membrane absorption method, which comprises the following steps:
step 1, feeding the desulfurization wastewater into an alkali adjusting tank, and adding an alkaline agent into the alkali adjusting tank through an alkaline agent adding device to adjust the pH value of the desulfurization wastewater to 11-13;
step 2, feeding the desulfurization wastewater into a heavy metal removal tank, adding organic sulfur into the heavy metal removal tank through an organic sulfur adding device, and stirring by using a second stirring device to remove heavy metals in the desulfurization wastewater;
step 3, the desulfurization wastewater from which the heavy metals are removed enters a clarification tank, and suspended matters in the desulfurization wastewater are removed through flocculation and clarification;
and 5, enabling the supernatant in the intermediate water tank to enter one side of a separation membrane in the membrane absorption assembly, separating ammonia gas in the desulfurization wastewater through the separation membrane, and enabling the separated ammonia gas to enter the other side of the separation membrane to be absorbed by the acidic absorption liquid, so that ammonia nitrogen in the desulfurization wastewater is removed.
As a further improvement of the invention, the sediment after the clarification action in the step 3 enters a sludge dewatering machine for dewatering treatment, and the dewatered filtrate water is conveyed to the soda adjusting tank 1 again for treatment.
As a further improvement of the invention, the method also comprises a step 6 of discharging the desulfurization wastewater after the ammonia nitrogen content in the desulfurization wastewater reaches the standard and adding acid to the desulfurization wastewater through an acid adding device to adjust the pH value of the desulfurization wastewater to 6-8.
The invention has the beneficial effects that: the method has the advantages of simple flow, less sludge production, high ammonia nitrogen removal efficiency, high ammonia nitrogen recovery rate, low running cost and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural diagram of a device for treating ammonia nitrogen in desulfurization wastewater by using a membrane absorption method according to an embodiment of the invention.
In the figure, the position of the upper end of the main shaft,
1. an alkali adjusting tank; 2. a first stirring device; 3. a weight removal pool; 4. a second stirring device; 5. a clarification tank; 6. a sludge dewatering machine; 7. a middle water tank; 8. a first water pump; 9. a membrane absorbent assembly; 10. a separation membrane; 11. an absorption liquid pool; 12. a second water pump; 13. a third stirring device; 14. an alkaline agent adding device; 15. an organic sulfur feeding device; 16. an acid adding device.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications (such as up, down, left, right, front, and back … …) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative positional relationship between the components, the movement situation, and the like in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indications are changed accordingly.
In addition, in the description of the present invention, the terms used are for illustrative purposes only and are not intended to limit the scope of the present invention. The terms "comprises" and/or "comprising" are used to specify the presence of stated elements, steps, operations, and/or components, but do not preclude the presence or addition of one or more other elements, steps, operations, and/or components. The terms "first," "second," and the like may be used to describe various elements, not necessarily order, and not necessarily limit the elements. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified. These terms are only used to distinguish one element from another. These and/or other aspects will become apparent to those of ordinary skill in the art in view of the following drawings, and the description of the embodiments of the present invention will be more readily understood by those of ordinary skill in the art. The drawings are only for purposes of illustrating the described embodiments of the invention. One skilled in the art will readily recognize from the following description that alternative embodiments of the structures and methods illustrated in the present application may be employed without departing from the principles described in the present application.
Embodiment 1, as shown in fig. 1, an apparatus for treating ammonia nitrogen in desulfurization wastewater by using a membrane absorption method according to an embodiment of the present invention includes:
the top end of the alkali adjusting tank 1 is provided with an alkaline agent adding device 14. The alkali adjusting tank 1 is a closed reactor, and an alkaline agent adding device 14 adds an alkaline agent to the desulfurization wastewater in the alkali adjusting tank 1 to ensure that the pH value of the desulfurization wastewater is 11-13 so as to ensure enough OH in the desulfurization wastewater-To ensure NH in the desulfurization wastewater4 +Can be sufficiently converted into NH3. The alkaline agent added can be calcium hydroxide or sodium hydroxide and the like, but is not limited to the two.
The top end of the heavy metal removal tank 3 is provided with an organic sulfur feeding device 15, the inlet end of the heavy metal removal tank 3 is connected with the outlet end of the alkali adjusting tank 1, and the outlet end of the heavy metal removal tank 3 is connected with the inlet end of the clarification tank 5. The heavy metal removal tank 3 is a closed reactor, and an organic sulfur adding device 15 adds organic sulfur to the desulfurization wastewater in the heavy metal removal tank 3 to enable the organic sulfur to react with heavy metals in the desulfurization wastewater, so that the heavy metals such as lead and mercury can be removed. The clarification tank 5 is a closed reactor, the desulfurization wastewater after the heavy metal removal is conveyed to the clarification tank 5 through overflow or a pipeline, a flocculating agent and coagulant aid adding device is arranged in the clarification tank 5, the flocculating agent and the coagulant aid are added to the desulfurization wastewater after the heavy metal removal, so that suspended matters in the wastewater can be precipitated and removed, and the suspended matters can simultaneously play a role of entrainment in the flocculation process to remove part of COD in the desulfurization wastewater.
And the inlet end of the middle water tank 7 is connected with the outlet end of the clarification tank 5, the outlet end of the middle water tank 7 is connected with the first inlet end of the membrane absorption assembly 9, and a separation membrane 10 is arranged inside the membrane absorption assembly 9. The intermediate water tank 7 is a closed reactor, and supernatant in the clarification tank 5 enters the membrane absorption assembly 9 through the intermediate water tank 7. The separation membrane 10 is a hydrophobic membrane, so that ammonia gas in the supernatant can be separated out and absorbed and removed by the absorption liquid on the other side of the separation membrane 10, and the purpose of removing ammonia nitrogen from the desulfurization wastewater is achieved.
And the inlet end of the absorption liquid pool 11 is connected with the first outlet end of the membrane absorption assembly 9, the outlet end of the absorption liquid pool 11 is connected with the second inlet end of the membrane absorption assembly 9, and the first inlet end and the second inlet end of the membrane absorption assembly 9 are respectively arranged at two sides of the separation membrane 10. The absorption liquid pool 11 is an acidic absorption liquid, and the mass concentration of an acidic absorbent is less than 2%. The acidic absorption liquid enters the membrane absorption assembly 9 through the second inlet end of the membrane absorption assembly 9, and after the acidic absorption liquid absorbs ammonia gas, the acidic absorption liquid flows back to the absorption liquid tank 11 through the first outlet end of the membrane absorption assembly 9. When the pH value of the acidic absorption liquid in the absorption liquid pool 11 is 6-8, the absorption liquid is discharged for utilization, and new absorption liquid is supplemented to repeat the membrane absorption process.
Further, a first stirring device 2 is arranged in the alkali adjusting tank 1, a second stirring device 4 is arranged in the heavy removing tank 3, and a third stirring device 13 is arranged in the absorption liquid tank 11. The first stirring device 2, the second stirring device 4 and the third stirring device 13 respectively play a role in stirring the solutions in the alkali exchange tank 1, the weight removal tank 3 and the hand sanitizer tank 11, so that the solutions in the alkali exchange tank, the weight removal tank 3 and the hand sanitizer tank 11 are uniformly mixed and then fully react.
Further, the bottom end of the clarification tank 5 is connected with the inlet end of the sludge dewatering machine 6, and the outlet end of the sludge dewatering machine 6 is connected with the inlet end of the alkali adjusting tank 1. And (3) the sediment generated by the suspended matters in the clarification tank 5 enters a sludge dewatering machine 6, the sediment is discharged after dewatering treatment for subsequent treatment, and filtrate water generated after dewatering returns to the alkali adjusting tank 1 to repeat the treatment process.
Further, a first water pump 8 is arranged between the outlet end of the middle water tank 7 and the first inlet end of the membrane absorption assembly 9; a second water pump 12 is arranged between the outlet end of the absorption liquid pool 11 and the second inlet end of the membrane absorption assembly 9. The first water pump 8 conveys the desulfurization wastewater in the middle water tank 7 to the membrane absorption assembly 9, and the second water pump 12 conveys the acidic absorption liquid in the absorption liquid tank 11 to the membrane absorption assembly 9.
Further, a waste liquid output pipeline is arranged at a second outlet end of the membrane absorption assembly 9, and an acid adding device 16 is arranged on the waste liquid output pipeline. When the ammonia nitrogen concentration in the desulfurization wastewater reaches the standard, the ammonia nitrogen concentration needs to be discharged, and before the ammonia nitrogen concentration is discharged, an acid agent needs to be added into the deamination wastewater through an acid adding device 16 to ensure that the pH value is between 6 and 8, and then the ammonia nitrogen concentration is discharged. Can set up PH detection device on waste liquid output pipeline in the application for carry out real-time detection to the PH of deamination waste water.
Furthermore, a multi-media filter is arranged between the outlet end of the clarification tank 5 and the inlet end of the middle water tank 7. The multi-media filter is used for filtering the supernatant in the clarification tank 5, and then conveying the filtered supernatant to the intermediate water tank 7, so that the concentration of suspended matters in the desulfurization wastewater entering the intermediate water tank 7 is ensured to be less than 5mg/L, and the separation membrane 10 is prevented from being polluted or the membrane pores of the separation membrane 10 are prevented from being blocked.
Further, the separation membrane 10 is a hydrophobic membrane, and the separation membrane 10 is one or more of a flat plate type, a hollow fiber type and a roll type. The separation membrane 10 is a hydrophobic membrane, so that ammonia gas in the desulfurization wastewater can be separated and absorbed and removed by the sulfurous acid absorption liquid on the other side of the separation membrane 10. Liquid water and other non-volatile substances in the desulfurization wastewater are trapped in the desulfurization wastewater, and the deaminated desulfurization wastewater flows back to the intermediate water tank 7. In application, the separation membrane 10 can be flat plate type, hollow fiber type or roll type, but is not limited to the hydrophobic membranes with the above structures, and the specific structure can be selected according to actual situations.
Embodiment 2, the present invention also provides a membrane absorption method for treating ammonia nitrogen in desulfurization wastewater, which comprises the following steps:
step 1, the desulfurization wastewater enters an alkali adjusting tank 1, and an alkaline agent is added into the alkali adjusting tank 1 through an alkaline agent adding device 14 to adjust the pH value of the desulfurization wastewater to 11-13. Enough hydroxide radicals are ensured to promote ammonium ions in the wastewater to be converted into molecular ammonia gas, and meanwhile, the PH of the desulfurization wastewater is adjusted to be alkaline, so that part of heavy metals in the desulfurization wastewater can be removed.
And 2, feeding the desulfurization wastewater into a heavy metal removal tank 3, adding organic sulfur into the heavy metal removal tank 3 through an organic sulfur adding device 15, and stirring by using a second stirring device 4 to remove heavy metals in the desulfurization wastewater. The organic sulfur agent reacts with heavy metals in the desulfurization wastewater, thereby removing heavy metal ions such as lead, mercury and the like.
And 3, the desulfurization wastewater from which the heavy metals are removed enters a clarification tank 5, and suspended matters in the desulfurization wastewater are removed through flocculation and clarification. Through flocculation clarification effect, get rid of the suspended solid in the desulfurization waste water, can get rid of partial COD in the desulfurization waste water through the effect of smuggleing secretly of suspended solid simultaneously.
And 4, filtering the supernatant in the clarification tank 5, and then feeding the filtered supernatant into the intermediate water tank 7 to ensure that the concentration of the suspended matters in the desulfurization wastewater in the intermediate water tank 7 is less than 5 mg/L.
And 5, enabling the supernatant in the intermediate water tank 7 to enter one side of a separation membrane 10 in a membrane absorption assembly 9, separating ammonia gas in the desulfurization wastewater through the separation membrane 10, and enabling the ammonia gas to enter the other side of the separation membrane 10 to be absorbed by acidic absorption liquid, so that ammonia nitrogen in the desulfurization wastewater is removed. The acidic absorption liquid in the absorption liquid pool 11 enters the membrane absorption assembly 9, and flows out of the membrane absorption assembly 9 after ammonia gas is absorbed and flows back to the absorption liquid pool 11. With the progress of deamination, when the pH value of the acidic absorption liquid in the absorption liquid pool 11 is 6-8, the absorption liquid is discharged for utilization, and new absorption liquid is supplemented to repeat the membrane absorption process.
Further, the sediment after the clarification action in the step 3 enters a sludge dewatering machine 6 for dewatering treatment, and the dewatered filtrate water is conveyed to the alkali adjusting tank 1 again for treatment.
Further, the method comprises a step 6 of discharging the desulfurization wastewater after the ammonia nitrogen content in the desulfurization wastewater reaches the standard and the pH of the desulfurization wastewater is adjusted to 6-8 by adding acid through an acid adding device 16.
In this application, the raw water of the desulfurization wastewater of a certain power plant (overflow of a wastewater cyclone), the used alkaline agent is lime milk, the acidic absorption liquid is a sulfuric acid solution, and the main water quality parameters of the used desulfurization wastewater are as follows:
index (I) | Unit of | Numerical value |
SS | mg/L | 4573 |
pH | mg/L | 6.1 |
Ammonia nitrogen | mg/L | 4736 |
TDS | mg/L | 24364 |
The desulfurization wastewater firstly enters an alkali adjusting tank 1, lime milk with the mass fraction of 3% is added into the alkali adjusting tank 1 through an alkaline agent adding device 14, the PH of the wastewater is adjusted to 12, after reaction for 30 minutes, the wastewater in the alkali adjusting tank 1 enters a heavy metal removing tank 3 through overflow, and organic sulfur is added into the heavy metal removing tank 3 to remove heavy metals such as mercury and lead in the wastewater.
After stirring and reacting for 30 minutes, the wastewater in the weight removal tank 3 enters a clarification tank 5 through overflow, polymeric ferric chloride and PAM (the concentration is 30mg/L and 6mg/L respectively) are added into the clarification tank 5, and suspended matters in the wastewater are removed through flocculation clarification. The sediment generated in the clarification tank 5 enters a sludge dewatering machine 6, and the filtrate water generated by the sludge dewatering machine 6 flows back to the alkali adjusting tank 1 to repeat the treatment process.
The concentration of suspended matter in the supernatant of the clarifier 5 was about 35 mg/L. In order to avoid pollution of the separation membrane 10, after supernatant liquid of the clarification tank 5 is filtered by a multi-media filter, the concentration of suspended matters in the wastewater is reduced to about 2mg/L, then the wastewater enters the intermediate water tank 7, the wastewater in the intermediate water tank 7 enters the membrane absorption assembly, ammonia in the wastewater in the membrane absorption assembly 9 volatilizes in the form of ammonia gas and permeates through the separation membrane 10, and 2% of sulfuric acid absorption liquid on the other side of the membrane is absorbed, so that the aim of removing the ammonia nitrogen is fulfilled. The sulfuric acid absorption liquid in the absorption liquid pool 11 enters the membrane absorption assembly 9, absorbs ammonia gas, flows out of the membrane absorption assembly 9, and flows back to the absorption liquid pool 11.
When the pH of the sulfuric acid absorption liquid in the absorption liquid pool 11 is 7, the absorption liquid is discharged for utilization, and new absorption liquid is supplemented to repeat the membrane absorption process. Experiments show that after membrane absorption treatment, the ammonia nitrogen concentration in the wastewater is reduced to 9mg/L, the removal rate exceeds 99.8 percent and is lower than the national first-grade discharge standard.
In the description provided herein, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Furthermore, those of ordinary skill in the art will appreciate that while some embodiments described herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims, any of the claimed embodiments may be used in any combination.
It will be understood by those skilled in the art that while the present invention has been described with reference to exemplary embodiments, various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The utility model provides a device of ammonia nitrogen in membrane absorption method treatment desulfurization waste water which characterized in that includes:
the top end of the alkali adjusting tank (1) is provided with an alkaline medicament adding device (14);
the top end of the heavy component removal tank (3) is provided with an organic sulfur adding device (15), the inlet end of the heavy component removal tank (3) is connected with the outlet end of the alkali adjusting tank (1), and the outlet end of the heavy component removal tank (3) is connected with the inlet end of the clarification tank (5);
the inlet end of the middle water tank (7) is connected with the outlet end of the clarification tank (5), the outlet end of the middle water tank (7) is connected with the first inlet end of a membrane absorption assembly (9), and a separation membrane (10) is arranged inside the membrane absorption assembly (9);
and the inlet end of the absorption liquid pool (11) is connected with the first outlet end of the membrane absorption assembly (9), the outlet end of the absorption liquid pool (11) is connected with the second inlet end of the membrane absorption assembly (9), and the first inlet end and the second inlet end of the membrane absorption assembly (9) are respectively arranged at two sides of the separation membrane (10).
2. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method according to claim 1, wherein a first stirring device (2) is arranged in the alkali adjusting tank (1), a second stirring device (4) is arranged in the heavy removal tank (3), and a third stirring device (13) is arranged in the absorption liquid tank (11).
3. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method as claimed in claim 1, wherein the bottom end of the clarification tank (5) is connected with the inlet end of a sludge dewatering machine (6), and the outlet end of the sludge dewatering machine (6) is connected with the inlet end of the soda adjusting tank (1).
4. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method according to claim 1, wherein a first water pump (8) is arranged between the outlet end of the intermediate water tank (7) and the first inlet end of the membrane absorption assembly (9); and a second water pump (12) is arranged between the outlet end of the absorption liquid pool (11) and the second inlet end of the membrane absorption assembly (9).
5. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method according to claim 1, wherein the second outlet end of the membrane absorption assembly (9) is further connected with a waste liquid output pipeline, and an acid adding device (16) is arranged on the waste liquid output pipeline.
6. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method according to claim 1, characterized in that a multi-media filter is arranged between the outlet end of the clarification tank (5) and the inlet end of the intermediate water tank (7).
7. The device for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption method according to claim 1, wherein the separation membrane (10) is a hydrophobic membrane, and the separation membrane (10) is one or more of a flat plate type, a hollow fiber type and a roll type.
8. A method for treating ammonia nitrogen in desulfurization waste water by a membrane absorption method of an apparatus for treating ammonia nitrogen in desulfurization waste water by a membrane absorption method according to any one of claims 1 to 7, which comprises the steps of:
step 1, feeding the desulfurization wastewater into an alkali adjusting tank (1), and adding an alkaline agent into the alkali adjusting tank (1) through an alkaline agent adding device (14) to adjust the pH value of the desulfurization wastewater to 11-13;
step 2, feeding the desulfurization wastewater into a heavy metal removal tank (3), feeding organic sulfur into the heavy metal removal tank (3) through an organic sulfur feeding device (15), and stirring by using a second stirring device (4) to remove heavy metals in the desulfurization wastewater;
step 3, the desulfurization wastewater from which the heavy metals are removed enters a clarification tank (5), and suspended matters in the desulfurization wastewater are removed through flocculation and clarification;
step 4, filtering the supernatant in the clarification tank (5) and then feeding the filtered supernatant into an intermediate water tank (7);
and 5, enabling the supernatant in the intermediate water tank (7) to enter one side of a separation membrane (10) in a membrane absorption assembly (9), separating ammonia gas in the desulfurization wastewater through the separation membrane (10), and enabling the ammonia gas to enter the other side of the separation membrane (10) to be absorbed by acidic absorption liquid, so that ammonia nitrogen in the desulfurization wastewater is removed.
9. The method for treating ammonia nitrogen in desulfurization wastewater by using the membrane absorption process as claimed in claim 8, wherein the precipitate obtained after the clarification in step 3 enters a sludge dewatering machine (6) for dewatering treatment, and the dewatered filtrate water is conveyed to the soda adjusting tank (1) again for treatment.
10. The method for treating ammonia nitrogen in desulfurization wastewater by membrane absorption according to claim 8, further comprising step 6, when the ammonia nitrogen content in the desulfurization wastewater reaches the standard, adding acid to the desulfurization wastewater by an acid adding device (16) to adjust the pH of the desulfurization wastewater to 6-8, and discharging.
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