CN106348374B - Deamination treatment method and treatment device for wastewater - Google Patents
Deamination treatment method and treatment device for wastewater Download PDFInfo
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- CN106348374B CN106348374B CN201610790891.4A CN201610790891A CN106348374B CN 106348374 B CN106348374 B CN 106348374B CN 201610790891 A CN201610790891 A CN 201610790891A CN 106348374 B CN106348374 B CN 106348374B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a deamination treatment method for wastewater, which adopts a treatment method for carrying out air stripping deamination and spraying ammonia recovery on the wastewater and comprises the steps of deamination and ammonia recovery treatment on the wastewater. According to the deamination treatment method for the wastewater, the pH value is used as a key regulation factor, the organic combination of all treatment links is realized, ammonia nitrogen pollutants in the wastewater are efficiently removed, the ammonia nitrogen content in the treated wastewater meets the requirement of a secondary emission standard in GB8978-1996 comprehensive wastewater emission standard, the removed ammonia nitrogen is converted into a reusable chemical product, and the method has remarkable benefits in economic value and environmental protection, so that the green chemical industry is realized. In addition, the treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, and the ammonia nitrogen removal treatment and recovery of the wastewater are conveniently and efficiently realized.
Description
Technical Field
The invention relates to the technical field of wastewater deamination, in particular to a deamination treatment method for wastewater and a treatment device for the treatment method.
Background
The influence of ammonia nitrogen pollution on the water body is serious, and the main effects are that the water body is rich in oxidation, algae propagation is promoted, a large amount of dissolved oxygen in water is consumed, aquatic organisms die, the water body is malodorous, and the like, so that the discharge of ammonia nitrogen in the sewage discharge standard has quite strict requirements. Common ammonia nitrogen removal methods in engineering include: ammonia stripping method, high temperature deamination method, microorganism method, break point chlorination method, ion exchange method, etc., wherein ammonia stripping method is a method for separating ammonia nitrogen wastewater by utilizing the gas-liquid equilibrium relation between the gas phase concentration and the liquid phase concentration of ammonia nitrogen, the ammonia nitrogen concentration is lower than 5000mg/L, but the ammonia nitrogen concentration of production wastewater in industrial production is often higher than 10000mg/L, the ideal treatment effect is difficult to achieve by adopting the common ammonia stripping method, and the removed substances often cause the problems of filling tower blockage, etc., therefore, the high-concentration ammonia nitrogen wastewater is treated by adopting the combined treatment process of high temperature deamination and stripping deamination, but the treatment process is complex, and the recovery treatment of ammonia nitrogen is insufficient after deamination.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a deamination treatment method for wastewater, which can remove high-content ammonia nitrogen pollution in the wastewater, ensure that the ammonia nitrogen content in the treated wastewater meets the requirement of a secondary emission standard in GB8978-1996 comprehensive wastewater emission standard, and can recover ammonia nitrogen to obtain ammonium sulfate.
In order to achieve the above object, the present invention provides a method for deaminizing wastewater, which is a method for treating wastewater by air stripping deamination and spraying recovered ammonia, comprising the steps of:
a. deamination treatment: adding NaOH solution into the wastewater, regulating the pH value, spraying, reversely contacting with air to perform air stripping deamination treatment, and discharging the deaminated wastewater; the pH value of the wastewater after deamination is controlled to be 10.5-11.5;
b. ammonia recovery treatment step: the gas escaping from the deamination treatment step is discharged after two-stage deamination absorption treatment, wherein the two-stage deamination absorption treatment comprises a first-stage deamination absorption treatment step of circularly spraying a first-stage deamination absorption liquid on the gas escaping from the deamination treatment step, and a second-stage deamination absorption treatment step of circularly spraying a second-stage deamination absorption liquid and a diluted sulfuric acid solution which is sprayed in a complementary manner on the gas escaping from the first-stage deamination absorption treatment step; controlling the pH value of the primary deamination absorption liquid to be 4.5-6.5, recovering the primary deamination absorption liquid, and sequentially carrying out evaporation concentration, crystallization and centrifugal desalination treatment on the recovered primary deamination absorption liquid to obtain a solid ammonium sulfide product; h in the dilute sulfuric acid solution 2 SO 4 The mass content of the ammonia absorption liquid is 30%, the second-stage deamination absorption liquid is a mixed solution obtained by ammonia absorption by recycling spraying after ammonia absorption is carried out in the second-stage deamination absorption treatment step by dilute sulfuric acid solution, and the first-stage deamination absorption liquid is prepared by the steps ofThe deamination absorption liquid is a mixed solution obtained by recycling and spraying ammonia absorption after ammonia absorption is carried out on the second-stage deamination absorption liquid in the first-stage deamination absorption treatment step.
In the treatment method, deamination treatment is firstly carried out on the wastewater, and NaOH solution is added into the wastewater to adjust the pH value of the wastewater, so that deamination treatment carried out by air sweeping the wastewater is realized on one hand, naOH is used as adjusting alkali to avoid the escape of impurity pollutants except ammonia pollutants in the air stripping process, and the ammonia recovery effect and the air treatment effect of the subsequent steps are ensured; on the other hand, the pH value of the wastewater after deamination is controlled to ensure the deamination effect of the wastewater, so that the ammonia nitrogen content in the wastewater is less than 25mg/L, and the requirement of the secondary emission standard in Table 4 of GB8978-1996 integrated wastewater emission standard is met. The pH value of the wastewater after deamination is maintained at 10.5-11.5 by regulating and controlling the amount of NaOH solution added into the wastewater with the pH value of the wastewater after deamination as a standard. The removed ammonia nitrogen pollutants are recycled along with air in an ammonia recycling process, and most ammonia is subjected to first-stage circulating spray absorption sequentially through a first-stage deamination absorption liquid to form a circulating absorption liquid mainly containing ammonium sulfate, and the rest ammonia is subjected to second-stage circulating spray absorption through a second-stage deamination absorption liquid and a supplemented dilute sulfuric acid solution to form a circulating absorption liquid mainly containing ammonium bisulfate; the pH value of the primary deamination absorption liquid is controlled to be maintained in the range of 4.5-6.5, and the supplementary spraying amount of the dilute sulfuric acid solution is regulated and controlled, so that the ammonia in the removed air is thoroughly absorbed, and the absorbed gas reaches the standard of malodorous pollutant emission standard (GB 14554-93); in addition, the mass content (30%) of the diluted sulfuric acid solution which is sprayed in a supplementing way and the pH value range (4.5-6.5) of the recovered primary deamination absorption liquid are limited, so that the recovered primary deamination absorption liquid reaches the ammonium sulfate concentration of 40%, namely a near-saturated solution, thereby meeting the standard of directly preparing solid ammonium sulfate and simultaneously avoiding the problem of crystal precipitation in an absorption tower.
According to the treatment method, the pH value is used as a key regulation factor, so that the organic combination of all treatment links is realized, the high-efficiency ammonia nitrogen removal treatment of the high-content ammonia nitrogen wastewater is finished on the premise of not introducing any substances, and the removed ammonia nitrogen is converted into a reusable chemical product, so that the treatment method has remarkable benefits in the aspects of economic value and environmental protection.
As a further limitation to the above manner, the step b is followed by a step of sequentially evaporating, concentrating, cooling, crystallizing and centrifugally dehydrating the recovered primary deamination absorption liquid to obtain a solid ammonium sulfide product.
The recovered first-stage deamination absorption liquid is subjected to evaporation concentration, cooling crystallization and centrifugal dehydration to directly obtain a solid ammonium sulfate product meeting the standard of a sales product, and the recovered first-stage deamination absorption liquid reaches a nearly saturated ammonium sulfate solution, so that energy can be greatly saved in the evaporation concentration process, and the product has higher economic value.
As a further limitation to the above mode, in the step a, the mass content of NaOH in the NaOH solution is 20-30%.
As a further limitation to the mode, in the step a, the air stripping and deamination treatment is two-stage air stripping and deamination treatment, the air-liquid ratio of air and wastewater in each stage of air stripping and deamination treatment is (3000-5000): 1, and the air tower flow rate of air is 1.0-2.0m/s.
As a further limitation of the above mode, in the step b, the gas-liquid ratio of the gas to the primary deamination absorption liquid is (30-100): 1; in the second-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the second-stage deamination absorption liquid is (30-100): 1.
Further limiting the operation parameters such as the gas-liquid ratio, the air tower flow rate, the gas-liquid ratio and the like of the air stripping deamination treatment process, and the deamination absorption treatment process in the treatment method, so that the deamination treatment reaches the optimal operation process, and further the treatment effect, the treatment cost and the like are excellent.
Meanwhile, the invention also provides a deamination treatment device for wastewater, which comprises a first pipeline mixer, a first deamination blowing tower, a first pipeline mixer and a second deamination blowing tower which are sequentially connected in series, wherein the first pipeline mixer and the first pipeline mixer are respectively connected with an alkali liquid tank through a first alkali adding metering pump and a second alkali adding metering pump; the liquid outlets of the first deamination blowing tower and the second deamination blowing tower are respectively provided with a first PH detector and a second PH detector, the first PH detector is in control connection with a first alkali adding metering pump, and the second PH detector is in control connection with a second alkali adding pump; the ammonia recycling unit comprises a first ammonia tail gas absorption tower and a second ammonia tail gas absorption tower which are connected in series and are respectively provided with a liquid storage tank and a spray header connected with the liquid storage tank through a circulating pump, the liquid storage tanks of the first ammonia tail gas absorption tower and the second ammonia tail gas absorption tower are communicated, an acid liquid supplementing spray header connected with an acid liquid tank through an acid adding pump is arranged on the second ammonia tail gas absorption tower, an overflow port is connected to the liquid storage tank of the first ammonia tail gas absorption tower, and the overflow port is connected with a first PH detector.
As a further limitation to the above manner, a liquid collecting tank is connected downstream of the overflow port of the first ammonia tail gas absorbing tower, and an evaporation concentrator, a crystallizer and a centrifuge are sequentially connected in series on the liquid collecting tank via a delivery pump.
As a further limitation of the above, a homogenizing tank is connected in series upstream of the first pipe mixer.
As a further limitation to the above manner, the acid make-up header is positioned above the header in the second ammonia tail gas absorption tower.
The treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, can conveniently and efficiently realize ammonia nitrogen removal treatment of wastewater, ensures that the treated wastewater meets the requirement of the secondary discharge standard in the table 4 of GB8978-1996 integrated wastewater discharge standard, and is more beneficial to converting the removed ammonia nitrogen into a reusable chemical product to realize recovery.
In summary, the method for deaminizing wastewater obtained by adopting the technical scheme of the invention adopts a mode of combining air stripping deamination and spraying ammonia recovery on wastewater, takes pH value as a key regulation factor, realizes the organic combination of each treatment link, efficiently removes high-content ammonia nitrogen pollution in wastewater on the premise of not introducing any substances, ensures that the ammonia nitrogen content in the treated wastewater reaches <25mg/L, namely, the requirement of the secondary discharge standard in the table 4 of GB8978-1996 integrated wastewater discharge standard, converts the removed ammonia nitrogen into reusable chemical products, has obvious benefits in economic value and environmental protection, and realizes green chemical industry. In addition, the treatment device provided by the invention is more beneficial to the operation and operation control of the treatment method, and can conveniently and efficiently realize ammonia nitrogen removal treatment and ammonia nitrogen recovery of wastewater.
Drawings
The invention will be described in more detail below with reference to the attached drawings and detailed description:
FIG. 1 is a schematic diagram of a deamination treatment device for wastewater according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an ammonia recovery unit according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a concentrating crystallization and centrifugation portion of a deaminated absorption liquid according to an embodiment of the present invention;
FIG. 4 is a schematic view of the structure of a first deamination blow-off tower of an embodiment of the present invention;
FIG. 5 is a schematic diagram of the mechanism of a second ammonia tail gas absorber according to an embodiment of the present invention;
in the figure: 1. a first pipe mixer; 2. a first deamination blow-off column; 3. a second pipe mixer; 4. a second deamination blow-off column; 5. an alkali solution tank; 6. a first alkali adding metering pump; 7. a second alkali adding metering pump; 8. a first pH detector; 9. a second pH detector; 10. a first ammonia tail gas absorption tower; 11. a second ammonia tail gas absorption tower; 12. adding an acid pump; 13. an acid liquid tank; 14. a third PH detector; 15. an overflow port; 16. an overflow port; 17. a chimney; 18. a liquid collecting tank; 19. a heat exchanger; 20. a transfer pump; 21. an evaporative concentrator; 22. a crystallizer; 23. a centrifuge; 24. a tower body; 25. a liquid inlet; 26. a spray header of the stripping tower; 27. a filler; 28. a liquid outlet; 29. an air outlet; 30. a blower; 31. a tower body; 32. a liquid storage tank; 33. an air inlet; 34. a filler; 35. a circulation spray header; 36. the alkali liquor is supplemented to the spray header; 37. and an air outlet.
Detailed Description
Examples
This example relates to deamination of high ammonia nitrogen wastewater.
The deamination treatment device of this embodiment, as shown in fig. 1 to 3, comprises a first pipeline mixer 1, a first deamination blowing tower 2 with a blower, a second pipeline mixer 3 and a second deamination blowing tower 4 with a blower which are connected in series in sequence, and a lift pump is also connected in series between the second pipeline mixer 3 and the first deamination blowing tower 2. The first pipeline mixer 1 and the second pipeline mixer 3 are respectively connected with an alkali solution tank 5 through a first alkali adding metering pump 6 and a second alkali adding metering pump 7, and alkali solution stored in the alkali solution tank 5 is respectively quantitatively added into the first pipeline mixer 1 and the second pipeline mixer 3 through the first alkali adding metering pump 6 and the second alkali adding metering pump 7 so as to regulate and control the pH value of wastewater in the first pipeline mixer 1 and the second pipeline mixer 3. After the wastewater is treated by the first ammonia removal blowing tower 2 and the second ammonia removal blowing tower 4 in sequence, the wastewater is discharged from an overflow port 15 connected to the bottom of the second ammonia removal blowing tower 4 to be sent into a sewage treatment station or municipal sewage pipe network.
A first PH detector 8 is additionally arranged at the liquid outlet of the first deamination blowing tower 2, and the first PH detector 8 is connected with and controls a first alkali adding metering pump 6 so as to regulate and control the first alkali adding metering pump 6 according to the pH value of the wastewater at the liquid outlet of the first deamination blowing tower 2, and further regulate and control the alkali adding amount into the first pipeline mixer 1. A second PH detector 9 is additionally arranged at the liquid outlet of the second deamination blow-off tower 4, and the second PH detector 9 is connected with and controls a second alkali adding metering pump 7 so as to regulate and control the second alkali adding metering pump 7 according to the pH value of the wastewater at the liquid outlet of the second deamination blow-off tower 4, thereby regulating and controlling the alkali adding amount into the second pipeline mixer 3.
The air outlets of the first ammonia removal blowing tower 2 and the second ammonia removal blowing tower 4 are connected in parallel to an ammonia recovery unit, the ammonia recovery unit comprises a first ammonia tail gas absorption tower 10 and a second ammonia tail gas absorption tower 11 which are connected in series, and the air outlet of the second ammonia tail gas absorption tower 11 is connected with a chimney 17. The first ammonia tail gas absorption tower 10 and the second ammonia tail gas absorption tower 11 are respectively provided with a liquid storage tank and a circulating spray header connected with the liquid storage tanks through a circulating pump arranged outside the tower, and the liquid storage tanks in the first ammonia tail gas absorption tower 10 and the second ammonia tail gas absorption tower 11 are also communicated. An acid liquor supplementing spray header is further arranged in the second ammonia tail gas absorption tower 11 and is connected to an acid liquor tank 13 through an acid adding pump 12 arranged outside the tower so as to be used for supplementing and spraying dilute sulfuric acid solution stored in the acid liquor tank 13 into the second ammonia tail gas absorption tower 11.
In order to fully exert the supplemental absorption effect of the dilute sulfuric acid solution, the acid liquid supplemental spray header is arranged above the circulating spray header in the second ammonia tail gas absorption tower 11. An overflow port 16 is connected to the liquid storage tank of the first ammonia tail gas absorbing tower 11 for discharging the absorbing solution in the first ammonia tail gas absorbing tower 11. A third PH detector 14 is additionally arranged at the overflow port 16, and the third PH detector 14 is connected with and controls the acid adding pump 12 so as to regulate and control the acid adding pump 12 according to the pH value of the primary deamination absorption liquid in the liquid storage tank of the first ammonia tail gas absorption tower 11, and further regulate and control the acid adding amount of the supplementary spray in the second ammonia tail gas absorption tower 11.
A liquid collecting tank 18 is connected to the downstream of the overflow port 16 of the first ammonia tail gas absorbing tower 11, a delivery pump 20 is connected to the outlet of the liquid collecting tank 18, a container with a hollow interior is used for collecting the absorbing solution discharged from the first ammonia tail gas absorbing tower 11 in the liquid collecting tank 18, and a centrifugal pump is used for the delivery pump 20. The outlet of the centrifugal pump 20 is connected in series with the heat exchanger 19, the evaporation concentrator 21, the crystallizer 22 and the centrifuge 23 in sequence, as shown in fig. 3, the heat exchanger 19 can be used for reutilizing the steam discharged from the evaporation concentrator 21, so as to make full use of the steam to avoid waste of the steam by emptying, and naturally, the heat exchanger 19 can also be removed in the embodiment. The evaporative concentrator 21 adopts an existing double-effect evaporative concentrator or triple-effect evaporative concentrator, the crystallizer 22 adopts an existing cooling crystallizer for cooling crystallization, and the centrifuge 23 adopts an existing industrial centrifuge. Wherein the centrifuge 23 discharged centrate may be transferred to the sump 18 for further processing.
In this embodiment, fig. 4 shows the structure of the first deamination blowing tower 2, and the structure of the second deamination blowing tower 4 is substantially the same as that of the first deamination blowing tower 2, and will not be described herein. As shown in fig. 4, the first deamination blowing tower 2 comprises a tower body 24, a blower 30 is connected to the bottom of the tower body 24, a liquid outlet 28 is arranged, an air outlet 29 is arranged at the top of the tower body 24, a filler 27 is arranged in the tower body 24, a blowing tower spray head 26 is arranged above the filler 27, the blowing tower spray head 26 is connected with a liquid inlet 25 arranged at the top of the tower body 24, and the liquid inlet 25 is connected with an upstream conveying pipeline.
Fig. 5 in this embodiment shows the structure of the second ammonia tail gas absorbing tower 11, which includes a tower body 31, a liquid storage tank 32 is arranged at the bottom of the tower body 31, an air inlet 33 is arranged above the liquid storage tank 32, a filler 34 is arranged above the air inlet 33, a circulation spray header 35 and an alkali liquor supplementing spray header 36 are arranged above the filler 34, the alkali liquor supplementing spray header 36 is higher than the circulation spray header 35, the circulation spray header 35 is connected to the liquid storage tank 32 through a circulation pump, the alkali liquor supplementing spray header 36 is connected to the acid liquor tank 13, and an air outlet 37 is further arranged at the top of the tower body 31. In this embodiment, the second ammonia tail gas absorbing tower 11 is basically the same as the first ammonia tail gas absorbing tower 10 except that no acid liquor supplementing spray header is provided, and the description thereof is omitted.
Example 1
Deamination of wastewater is performed in the treatment device, wastewater (ammonia nitrogen content is more than 5000 mg/L) is input into a homogenizing tank, and then the following treatment is performed:
a. deamination treatment: aiming at the characteristic of ammonia nitrogen content in wastewater, the wastewater output from a homogenizing tank can be subjected to two-stage air stripping deamination treatment to completely remove ammonia nitrogen pollution, the pH value of the wastewater is adjusted by adding NaOH solution (the mass content is 20% -30%) into a first pipeline mixer, the wastewater is uniformly mixed and then is input into a first deamination blowing tower for spraying, the sprayed wastewater is reversely contacted with air blown from a blower in the tower to be subjected to first-stage air stripping deamination treatment, then is conveyed to the first pipeline mixer from a liquid outlet of the first deamination blowing tower to be adjusted by adding NaOH solution, the mixed and then is input into a second deamination blowing tower for spraying, the sprayed wastewater is reversely contacted with air blown from the blower in the tower to be subjected to second-stage air stripping deamination treatment, and the wastewater reaches the second-stage discharge standard of GB8978-1996 comprehensive wastewater discharge standard table 4 after the two-stage air stripping deamination treatment, so that the wastewater is treated and can be discharged to municipal wastewater pipe network; the treatment process controls a first alkali adding metering pump according to the numerical value detected by a first PH detector to control the adding amount of NaOH solution in a first pipeline mixer, controls a second alkali adding metering pump according to the numerical value detected by a second PH detector to control the adding amount of NaOH solution in the first pipeline mixer, and further controls the pH value of wastewater after deamination (namely the numerical values detected by the first PH detector and the second PH detector) to be maintained at 10.5-11.5;
b. ammonia recovery treatment step: the gas escaping from the gas outlet of the first deamination blowing tower and the gas outlet of the second deamination blowing tower is jointly input into an ammonia recovery unit for two-stage deamination absorption treatment, the gas firstly enters the first ammonia tail gas absorption tower and is subjected to the first-stage deamination absorption treatment by the circulating sprayed first-stage deamination absorption liquid, then enters the second ammonia tail gas absorption tower and is subjected to the second-stage deamination absorption treatment by the circulating sprayed second-stage deamination absorption liquid and the supplemented sprayed dilute sulfuric acid solution (the mass content is 30 percent), and the gas escaping from the gas outlet of the second ammonia tail gas absorption tower reaches the malodorous pollutant emission standard (GB 14554-93) and can be directly discharged as the atmosphere; the treatment process comprises the steps of controlling the spraying quantity of dilute sulfuric acid solution sprayed by an acid liquor replenishing spray header in a second ammonia tail gas absorption tower according to the pH value of the first ammonia tail gas absorption liquid detected by a third pH detector, controlling the pH value of the first ammonia tail gas absorption liquid to be 4.5-6.5, recovering the first ammonia tail gas absorption liquid through an overflow port of the first ammonia tail gas absorption tower, wherein the recovered first ammonia tail gas absorption liquid is nearly saturated solution of ammonium sulfate, the mass content of the ammonium sulfate is 40%, the problem of crystal precipitation in the absorption tower is avoided, further treating the recovered first ammonia tail gas absorption liquid, evaporating and concentrating the first ammonia tail gas absorption liquid collected in a liquid collecting tank through a concentrating and evaporating crystallizer, cooling and crystallizing in a cooling crystallizer, and finally conveying the first ammonia tail gas absorption liquid to a centrifugal machine for centrifugal dehydration to obtain solid ammonium sulfate which can meet the standards of ammonium sulfate sales products, returning the solution obtained through centrifugation of the centrifugal machine to a liquid collecting tank for concentration and crystallization, and recycling ammonia; the secondary deamination absorption liquid is a mixed solution which is mainly composed of sulfuric acid and ammonium bisulfate and is obtained by ammonia absorption of dilute sulfuric acid solution in a second ammonia tail gas absorption tower and then recycling spraying, and the primary deamination absorption liquid is a mixed solution which is mainly composed of ammonium sulfate and is obtained by ammonia absorption of the secondary deamination absorption liquid in a first ammonia tail gas absorption tower and then recycling spraying.
In the treatment method, in the step a, the gas-liquid ratio of the air and the wastewater in the first deamination blowing tower and the second deamination blowing tower is (3000-5000) 1 (m 3 /m 3 ) The air flow rate of the air tower is 1.0-2.0m/s; in the step b, the gas-liquid ratio of the first ammonia tail gas absorption tower (i.e. the ratio of the gas which escapes after the deamination treatment step to the primary deamination absorption liquid) is (30-100) 1 (m 3 /m 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The gas-liquid ratio of the second ammonia tail gas absorption tower (i.e. the ratio of the gas which escapes after the first-stage deamination absorption treatment step to the second-stage deamination absorption liquid) is (30-100) 1 (m 3 /m 3 )。
After detection, the treated wastewater NH 3 -N<25mg/L, meets the secondary discharge standard of Table 4 of GB8978-1996 Integrated wastewater discharge Standard
Contaminant content ammonia in gas<100mg/m 3 Meets the emission standard of malodorous pollutants (GB 14554-93).
Example 2
This example relates to the effect of different control conditions on wastewater and gas treatment results in the treatment process of example 1.
Example 2.1
The same treatment device and the same treatment method as in example 1 are adopted to treat high-content ammonia nitrogen wastewater (the ammonia nitrogen content in the original wastewater is 15329 mg/L), the influence of pH control conditions on wastewater and gas treatment results is detected under the same other operation conditions, and the experiment and the results are shown in the following table:
as can be seen from the table, in the deamination treatment method for wastewater, the pH value control of three links is critical to deamination treatment, the pH value of wastewater after the first deamination blowing-off tower and the second deamination blowing-off tower is controlled to be more than 10.5, the pH value of liquid at the overflow port of the first ammonia tail gas absorbing tower is controlled to be less than 6.5, high-content ammonia nitrogen pollution in the wastewater can be thoroughly treated, the secondary emission standard in the table 4 of GB8978-1996 comprehensive wastewater emission standard is reached, and removed ammonia is converted into a reusable chemical product, so that high-efficiency recovery is realized.
Example 2.2
The same treatment device and the same treatment method as in example 1 are adopted to treat high-content ammonia nitrogen wastewater (the ammonia nitrogen content in the original wastewater is 15329 mg/L), the influence of control conditions such as air flow rate and gas-liquid ratio on wastewater and gas treatment results are detected under the same other operation conditions, and the experiment and the results are shown in the following table:
as can be seen from the table, in the deamination treatment method for wastewater, conditions such as air flow rate and gas-liquid ratio can influence the deamination treatment result for wastewater.
Comparative example
The comparative example relates to the comparison of the treatment method of high-content ammonia nitrogen wastewater (the ammonia nitrogen content of the original wastewater is 15329 mg/L) and the deamination treatment method of wastewater in the prior art.
In the prior art, the pH value before the stripping tower is controlled, and the treatment results are shown in the following table:
in the existing stripping ammonia method, the pH value is regulated and controlled before a stripping ammonia stripping tower, and as ammonia is an alkaline substance, after part of ammonia is stripped off in a gas form, the pH value of liquid in the tower is reduced, and especially for wastewater with ammonia nitrogen content above 5000mg/L, the ammonia nitrogen content of the discharged water is not easy to control. In addition, in the prior art, the concentration of ammonium sulfate in the ammonia absorption tower is easy to be too high and reaches more than 43%, so that crystallization occurs in the tower, the tower body is blocked due to scaling of the filler in the tower, and the absorption tower is lost.
As can be seen by comparing the treatment results of the comparative example with those of the example 1, the ammonia nitrogen removal treatment method for wastewater can efficiently and stably remove high-content ammonia nitrogen pollution in wastewater, and convert the removed ammonia nitrogen into reusable chemical products, has remarkable benefits in the aspects of economic value and environmental protection, and realizes green chemical industry.
Claims (2)
1. A deamination treatment method for wastewater is characterized by adopting a treatment method for carrying out air stripping deamination and spraying recycling of ammonia on the wastewater, and comprising the following steps of:
a. deamination treatment: adding NaOH solution into the wastewater, regulating the pH value, spraying, reversely contacting with air to perform air stripping deamination treatment, and discharging the deaminated wastewater; the pH value of the deaminated wastewater is controlled to be 10.5-11.5; the mass content of NaOH in the NaOH solution is 20-30%;
in the step a, the air stripping and deamination treatment is two-stage air stripping and deamination treatment, the air-liquid ratio of air and wastewater in each stage of air stripping and deamination treatment process is (3000-5000): 1, and the air tower flow rates of the air are (1.0-2.0) m/s;
b. ammonia recovery treatment step: the gas escaping from the deamination treatment step is discharged after two-stage deamination absorption treatment, wherein the two-stage deamination absorption treatment comprises a first-stage deamination absorption treatment step of circularly spraying a first-stage deamination absorption liquid on the gas escaping from the deamination treatment step, and a second-stage deamination absorption treatment step of circularly spraying a second-stage deamination absorption liquid and a diluted sulfuric acid solution which is sprayed in a complementary manner on the gas escaping from the first-stage deamination absorption treatment step;
the removed ammonia nitrogen pollutants enter an ammonia recovery treatment process along with air in the form of ammonia gas, and the ammonia gas is subjected to primary circulating spray absorption on most ammonia gas sequentially through primary deamination absorption liquid to form circulating absorption liquid mainly containing ammonium sulfate, and then the residual ammonia gas is subjected to secondary circulating spray absorption on the rest small amount of ammonia gas through secondary deamination absorption liquid and supplemented dilute sulfuric acid solution to form circulating absorption liquid mainly containing ammonium bisulfate; the pH value of the primary deamination absorption liquid is controlled to regulate and control the supplementary spraying quantity of the dilute sulfuric acid solution;
controlling the pH value of the primary deamination absorption liquid to be 4.5-6.5, and recovering the primary deamination absorption liquid; h in the dilute sulfuric acid solution 2 SO 4 The mass content of the ammonia-absorbing liquid is 30%, the ammonia-absorbing liquid is a mixed solution obtained by ammonia absorption by recycling spraying after ammonia absorption is carried out on the dilute sulfuric acid solution in the second-stage ammonia-absorbing treatment step, and the ammonia-absorbing liquid is a mixed solution obtained by ammonia absorption by recycling spraying after ammonia absorption is carried out on the second-stage ammonia-absorbing liquid in the first-stage ammonia-absorbing treatment step;
in the step b, in the first-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the first-stage deamination absorption liquid is (30-100): 1; in the second-stage deamination absorption treatment process, the gas-liquid ratio of the gas to the second-stage deamination absorption liquid is (30-100): 1; the recovered first-stage deamination absorption liquid reaches the concentration of ammonium sulfate of 40 percent, and meets the standard of directly preparing solid ammonium sulfide.
2. The deamination treatment method of wastewater according to claim 1, wherein: and b, sequentially carrying out evaporation concentration, cooling crystallization and centrifugal dehydration on the recovered primary deamination absorption liquid to obtain a solid ammonium sulfide product.
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| CN107434291A (en) * | 2017-09-05 | 2017-12-05 | 浙江南化防腐设备有限公司 | One kind reclaims high strength ammonia water system from ammonia nitrogen waste water |
| CN107585815A (en) * | 2017-09-30 | 2018-01-16 | 浦湘生物能源股份有限公司 | A kind of high-concentration ammonia nitrogenous wastewater cooperates with the method and system administered with flue gas of refuse burning NOx pollutants |
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| CN111924998A (en) * | 2019-05-13 | 2020-11-13 | 自然资源部天津海水淡化与综合利用研究所 | Closed-cycle efficient recycling ammonia nitrogen removal equipment and method |
| CN111748012A (en) * | 2020-06-22 | 2020-10-09 | 广东闻扬环境科技有限公司 | Device and method for recovering ammonium from ammonian-containing stock solution and concentrating protein stock solution |
| CN113262616B (en) * | 2020-12-17 | 2022-06-24 | 合肥恒力装备有限公司 | Recycling treatment process for ammonia-containing tail gas |
| CN112794339B (en) * | 2020-12-25 | 2022-08-05 | 中国科学院城市环境研究所 | Method and device for recovering ammonia in liquid |
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