CN114477558A - Ammonia-removing treatment method for ammonia nitrogen wastewater - Google Patents
Ammonia-removing treatment method for ammonia nitrogen wastewater Download PDFInfo
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000002351 wastewater Substances 0.000 title claims abstract description 183
- 238000000034 method Methods 0.000 title claims abstract description 90
- 230000003204 osmotic effect Effects 0.000 claims abstract description 80
- 230000009615 deamination Effects 0.000 claims abstract description 72
- 238000006481 deamination reaction Methods 0.000 claims abstract description 72
- 239000000203 mixture Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 109
- 229910021529 ammonia Inorganic materials 0.000 claims description 52
- 239000012528 membrane Substances 0.000 claims description 51
- 238000009834 vaporization Methods 0.000 claims description 37
- 230000008016 vaporization Effects 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005373 pervaporation Methods 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000000149 chemical water pollutant Substances 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
-
- 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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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)
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- Organic Chemistry (AREA)
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Abstract
The invention provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps: adjusting the pH of the ammonia nitrogen wastewater to be treated, and then carrying out air stripping to obtain primary ammonia nitrogen wastewater; carrying out steam stripping and stripping on the primary ammonia nitrogen wastewater to obtain secondary ammonia nitrogen wastewater; and performing osmotic deamination on the secondary ammonia nitrogen wastewater to obtain treated ammonia nitrogen wastewater. The method adopts a combined process to carry out deamination treatment according to the composition of the ammonia nitrogen wastewater, and the combined process sequentially adopts air stripping, steam stripping and osmotic deamination methods, so that the ammonia nitrogen in the wastewater can adopt proper treatment processes at different concentrations to realize higher ammonia nitrogen removal rate; the method is simple to operate, low in cost, suitable for treating various types of wastewater containing ammonia nitrogen, large in treatment capacity and free of secondary pollution.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a method for ammonia nitrogen wastewater deamination treatment.
Background
As common water and atmosphere pollution, ammonia nitrogen pollution can cause great harm to human health and ecological environment, ammonia nitrogen is one of main oxygen-consuming pollutants in water, and if the ammonia nitrogen is directly discharged into the water, eutrophication of the water is easily caused. The ammonia nitrogen wastewater has large production amount, mainly comprises industrial wastewater and domestic sewage, wherein the industrial wastewater is from the industries of petrochemical industry, metallurgy, pharmacy, chemical fertilizer, electronics and the like, in addition, the ammonia nitrogen wastewater also comprises secondary effluent of a garbage treatment plant and the like, and the ammonia nitrogen-containing wastewater can be discharged after being treated by adopting an ammonia nitrogen removal technology.
At present, common ammonia nitrogen removal methods include a biological method, a stripping and stripping method, a chemical precipitation method, a breakpoint chlorination method, a support gas membrane method and the like. The biological denitrification method is the most common method, mainly utilizes microorganisms to convert ammonia nitrogen substances in water into nontoxic and harmless nitrogen under the biochemical treatment effects of anaerobic treatment, anoxic treatment, aerobic treatment and the like, has higher requirements on the quality of wastewater, and is not suitable for denitrification of industrial wastewater with low organic matters, high concentration, high salinity and difficult degradation; the ammonia stripping and steam stripping process has simple flow and stable treatment effect, but has large energy consumption and higher cost, is easy to cause secondary pollution, and needs to be frequently disassembled and cleaned; the chemical precipitation method and the breakpoint chlorination method can effectively remove ammonia nitrogen in the wastewater, but new compounds are introduced, so that secondary pollution is possibly caused, and the reusability of the wastewater is influenced; the supported gas membrane method can sufficiently reduce the ammonia nitrogen concentration, but generally, the permeation phenomenon of water is serious, and it is difficult to obtain a desired byproduct.
CN 101318752A discloses an ammonia nitrogen wastewater recycling treatment method and a device, and the method comprises the following steps: adjusting the pH value of the ammonia nitrogen wastewater in an automatic dosing device, and preheating the ammonia nitrogen wastewater in a preheating device; water is uniformly distributed by a spraying device in a removal section and collected in a bottom liquid storage area, ammonia is blown off by adopting forced air, the wastewater is repeatedly removed with ammonia in a circulating spraying system, and the wastewater is discharged by a water outlet weir after being purified; the ammonia-containing waste gas is filtered by the demisting device and then is subjected to multi-stage spray absorption to form an ammonia crude product for recycling, and the purified gas is emptied from the top. The method mainly adopts the blowing and spraying operation, does not adopt a mode of combining various processes, has limited ammonia nitrogen removal rate and is suitable for treating less types of waste water.
CN 108706672A discloses a resource treatment method of ammonia nitrogen wastewater, which comprises the following steps: adjusting the pH value of the ammonia nitrogen wastewater to 10-12, degassing by adopting a deamination film, and absorbing by acid liquor to obtain deamination wastewater and an ammonia salt solution; introducing air into the ammonia salt solution for stripping to obtain stripping residual liquid I and ammonia-containing mixed gas I; absorbing the ammonia-containing mixed gas I by adopting absorption liquid through a shell pass to obtain ammonia water; introducing air into the ammonia water for stripping to obtain stripping residual liquid II and ammonia-containing mixed gas II; and (4) absorbing the ammonia-containing mixed gas II by the ammonia water obtained in the last step to obtain the ammonia water with high quality and concentration. The method only adopts deaminizing membrane to degas and then absorb the ammonia nitrogen wastewater, and the subsequent treatment is the treatment of the ammonia salt solution obtained after ammonia gas absorption, which is equivalent to that only one-time deaminizing treatment is carried out on the initial waste liquid, and no combined process deaminizing is carried out on the ammonia nitrogen wastewater, so that the ammonia nitrogen removal rate is low, and the influence of the type of the wastewater is large.
In conclusion, for the treatment of the ammonia nitrogen wastewater, a proper combination process and a proper sequence thereof are selected according to the composition of the wastewater and the ammonia nitrogen content, so that the ammonia nitrogen wastewater is suitable for treating the wastewater with corresponding concentration, the total treatment cost is low, and the ammonia nitrogen removal rate is high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for ammonia nitrogen wastewater deamination treatment, which adopts a combined process to perform deamination treatment according to the composition of ammonia nitrogen wastewater, wherein the combined process sequentially adopts air stripping, steam stripping and osmotic deamination methods, so that ammonia nitrogen in wastewater can adopt proper treatment processes at different concentrations to achieve higher ammonia nitrogen removal rate, and meanwhile, the method has the advantages of low overall cost, large treatment capacity and no secondary pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of the ammonia nitrogen wastewater to be treated, and then carrying out air stripping to obtain primary ammonia nitrogen wastewater;
(2) carrying out steam stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1) to obtain secondary ammonia nitrogen wastewater;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2) to obtain treated ammonia nitrogen wastewater.
In the invention, for the treatment of ammonia nitrogen wastewater, when the concentration of ammonia nitrogen in the wastewater is higher, a single treatment method is often difficult to fully remove ammonia nitrogen, so a combined process is usually adopted, a proper combined process is selected according to the composition and concentration of the ammonia nitrogen wastewater, the wastewater is firstly adjusted to the pH value suitable for ammonia removal, an air stripping mode is firstly adopted when the content of ammonia nitrogen is higher, the operation is simple and convenient, the cost is lower, a large amount of ammonia nitrogen is removed, then stripping is adopted, the ammonia in the wastewater is further taken out by utilizing the characteristics of steam temperature and the like, and finally, an osmotic vaporization mode is adopted for deamination, the selection of the combination and the sequence of the operations are all selected within the ammonia nitrogen concentration range suitable for treatment, the operation in each step is simpler, the cost is lower, the removal rate of ammonia nitrogen is high, and the residual components can be recycled; the method has high treatment rate and treatment capacity for wastewater, is suitable for treating various wastewater containing ammonia nitrogen, and does not cause secondary pollution.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred technical scheme of the invention, the source of the ammonia nitrogen wastewater to be treated in the step (1) comprises any one or a combination of at least two of landfill leachate, ammonia-containing waste gas treatment absorption liquid or ammonium-containing waste liquid generated by smelting, and typical but non-limiting examples of the combination are as follows: the combination of the landfill leachate and the ammonia-containing waste gas treatment absorption liquid, the combination of the ammonia-containing waste gas treatment absorption liquid and the ammonium-containing waste liquid generated by smelting, the combination of the landfill leachate, the ammonia-containing waste gas treatment absorption liquid and the ammonium-containing waste liquid generated by smelting and the like.
Preferably, the ammonia nitrogen content in the ammonia nitrogen wastewater to be treated in the step (1) is 10-100 g/L, such as 10g/L, 30g/L, 50g/L, 60g/L, 80g/L or 100g/L, etc., but not limited to the recited values, and other unrecited values in the range of the values are also applicable.
Preferably, the composition of the ammonia nitrogen wastewater to be treated in the step (1) comprises any one or a combination of at least two of ammonium sulfate, ammonium carbonate or ammonium chloride, and the combination is typically but not limited to: a combination of ammonium sulfate and ammonium carbonate, a combination of ammonium carbonate and ammonium chloride, a combination of ammonium sulfate, ammonium carbonate and ammonium chloride, and the like.
In a preferred embodiment of the present invention, the pH adjustment in step (1) is performed to adjust the pH of the ammonia nitrogen wastewater to 10-14, for example, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5 or 14, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, the purpose of adjusting the pH value of the ammonia nitrogen wastewater before treatment is to ensure that ammonia nitrogen mainly adopts NH3In a form convenient for subsequent NH3And (4) removing.
Preferably, the air stripping in the step (1) is air circulation stripping.
Preferably, the temperature of the air stripping in step (1) is 20 to 50 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the air stripping time in step (1) is 0.5-2 h, such as 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h or 2h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As the preferable technical scheme of the invention, the ammonia blown out by the air in the step (1) is absorbed by water and recovered to obtain ammonia water.
Preferably, the ammonia nitrogen content of the primary ammonia nitrogen wastewater in the step (1) is 1-5 g/L, such as 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5g/L, but not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the stripping in the step (2) is stripping by adopting steam.
Preferably, the stripping temperature in step (2) is 85 to 105 ℃, for example 85 ℃, 90 ℃, 95 ℃, 100 ℃ or 105 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stripping and stripping time in step (2) is 0.1-0.5 h, such as 0.1h, 0.2h, 0.25h, 0.33h, 0.4h, 0.45h or 0.5h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
According to the invention, the steam temperature is higher during stripping and stripping, because the contact time with the wastewater is short, a small amount of steam is cooled to become a liquid phase, most ammonia is still taken out in a gas phase form, and the ammonia is firstly subjected to heat exchange with the air in the step (1) before being absorbed by water, so that the temperature of the air is increased, and the removal amount of the ammonia during air stripping can be increased.
As a preferable technical scheme of the invention, the steam and the brought-out ammonia after the stripping and stripping in the step (2) exchange heat with the air used for the stripping in the step (1) and then are absorbed by water.
Preferably, the ammonia nitrogen content of the secondary ammonia nitrogen wastewater in the step (2) is 200-800 ppm, such as 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm or 800ppm, but not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the osmotic deamination in the step (3) is processed by adopting a pervaporation membrane.
Preferably, the temperature of the osmotic deamination in step (3) is 20 to 40 ℃, for example 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the pressure difference between both sides of the pervaporation membrane at the time of the osmotic deamination is 0.1 to 0.5MPa, for example, 0.1MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa or 0.5MPa, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
In the process of the osmotic deamination, the permeation of the ammonia gas takes the gas partial pressure difference at two sides of the pervaporation membrane as a driving force.
In a preferred embodiment of the present invention, the pervaporation membrane is made of any one of ceramics, polyvinyl chloride (PVC) and polyvinyl alcohol (PVA), and the kind of the ceramics includes aluminosilicate and boroaluminate.
Preferably, during the pervaporation, ammonia molecules pass through the pervaporation membrane to enter the other side and are absorbed by acid liquor, the pressure difference between the two sides of the pervaporation membrane is maintained, and liquid molecules do not penetrate through the pervaporation membrane, so that the pervaporation process is normally carried out.
As a preferred embodiment of the present invention, the ammonia nitrogen content in the ammonia nitrogen wastewater after the treatment in step (3) is reduced to below 15ppm, such as 15ppm, 12ppm, 10ppm, 8ppm, 6ppm, 4ppm or 2ppm, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the composition of the ammonia nitrogen wastewater treated in the step (3) comprises sodium sulfate and/or sodium chloride.
In the invention, after the ammonia nitrogen wastewater is deaminated, the solution after treatment basically contains no ammonia or ammonium ions according to the type of alkali used in pH adjustment, and the cation mainly contains sodium ions or potassium ions.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the ammonia nitrogen content of the ammonia nitrogen wastewater to be treated is 10-100 g/L, the ammonia nitrogen wastewater comprises any one or the combination of at least two of ammonium sulfate, ammonium carbonate or ammonium chloride, the pH value is adjusted to 10-14, then air stripping is carried out, the air stripping temperature is 20-50 ℃, the time is 0.5-2 h, primary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 1-5 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and air stripping is carried out by adopting steam, the stripping and air stripping temperature is 85-105 ℃, and the time is 0.1-0.5 h, so as to obtain secondary ammonia nitrogen wastewater, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 200-800 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 20-40 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.1-0.5 MPa, the material of the osmotic vaporization membrane comprises any one of ceramics, polyvinyl chloride or polyvinyl alcohol, ammonia molecule ammonia passes through the osmotic vaporization membrane to enter the other side during the osmotic deamination, the ammonia molecule ammonia is absorbed by acid liquor to maintain the pressure difference between two sides of the osmotic vaporization membrane, the rest is the processed ammonia nitrogen wastewater, and the ammonia nitrogen content in the processed ammonia nitrogen wastewater is reduced to below 15 ppm.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts a combined process to carry out deamination treatment according to the composition of the ammonia nitrogen wastewater, and the combined process sequentially adopts air stripping, steam stripping and osmotic deamination methods, so that the ammonia nitrogen in the wastewater can adopt proper treatment processes at different concentrations to realize higher ammonia nitrogen removal rate which can reach more than 99.9 percent;
(2) the method disclosed by the invention is simple to operate, low in cost, suitable for treating various types of wastewater containing ammonia nitrogen, large in treatment capacity and free from secondary pollution.
Drawings
FIG. 1 is a process flow diagram of a method for ammonia nitrogen wastewater deamination treatment provided in embodiment 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of the ammonia nitrogen wastewater to be treated, and then carrying out air stripping to obtain primary ammonia nitrogen wastewater;
(2) carrying out steam stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1) to obtain secondary ammonia nitrogen wastewater;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2) to obtain treated ammonia nitrogen wastewater.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a method for ammonia nitrogen wastewater deamination treatment, wherein a process flow chart of the method is shown in figure 1, and the method comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the source of the ammonia nitrogen wastewater to be treated is landfill leachate, the content of ammonia nitrogen in the ammonia nitrogen wastewater is 50g/L, the composition of the ammonia nitrogen wastewater comprises ammonium sulfate, adjusting the pH value to 12, and then carrying out air stripping at the temperature of 35 ℃ for 1h to obtain primary ammonia nitrogen wastewater, wherein the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 3 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and air stripping is carried out by adopting steam, the stripping and air stripping temperature is 95 ℃, the time is 0.3h, and secondary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 400 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 30 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.3MPa, the osmotic vaporization membrane is made of polyvinyl chloride, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by sulfuric acid during the osmotic deamination, the rest is processed ammonia nitrogen wastewater, and the ammonia nitrogen content of the processed ammonia nitrogen wastewater is reduced to 12 ppm.
According to the invention, through the combined deamination treatment process, the deamination rate of the ammonia nitrogen wastewater is high and can reach 99.97%; the method has low cost and no secondary pollution.
Example 2:
the embodiment provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the source of the ammonia nitrogen wastewater to be treated is ammonia-containing waste gas treatment absorption liquid, the ammonia nitrogen content of the ammonia nitrogen wastewater is 10g/L, the ammonia nitrogen wastewater comprises ammonium sulfate, the pH value is adjusted to 10, then air stripping is carried out, the air stripping temperature is 50 ℃, the time is 0.5h, primary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 1 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and stripping are carried out by adopting steam, the stripping and stripping temperature is 105 ℃, the time is 0.16h, and secondary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 200 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 40 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.1MPa, the osmotic vaporization membrane is made of polyvinyl alcohol, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by sulfuric acid during the osmotic deamination, the rest is processed ammonia nitrogen wastewater, and the ammonia nitrogen content in the processed ammonia nitrogen wastewater is reduced to 5 ppm.
According to the invention, through the combined deamination treatment process, the deamination rate of the ammonia nitrogen wastewater is high and can reach 99.95%; the method has low cost and no secondary pollution.
Example 3:
the embodiment provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the source of the ammonia nitrogen wastewater to be treated is ammonium-containing waste liquid generated by smelting, the content of ammonia nitrogen in the ammonia nitrogen wastewater is 100g/L, the composition of the ammonia nitrogen wastewater comprises ammonium sulfate and ammonium chloride, adjusting the pH value to 14, and then performing air stripping at the temperature of 20 ℃ for 2h to obtain primary ammonia nitrogen wastewater, wherein the content of ammonia nitrogen in the primary ammonia nitrogen wastewater is 5 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and air stripping is carried out by adopting steam, the stripping and air stripping temperature is 85 ℃, the time is 0.5h, and secondary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 600 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 20 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.5MPa, the osmotic vaporization membrane is made of aluminosilicate ceramic, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by sulfuric acid during the osmotic deamination, the rest is processed ammonia nitrogen wastewater, and the ammonia nitrogen content in the processed ammonia nitrogen wastewater is reduced to 15 ppm.
According to the invention, through the combined deamination treatment process, the deamination rate of the ammonia nitrogen wastewater is high and can reach 99.98%; the method has low cost and no secondary pollution.
Example 4:
the embodiment provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the source of the ammonia nitrogen wastewater to be treated is landfill leachate, the ammonia nitrogen content of the ammonia nitrogen wastewater is 30g/L, the ammonia nitrogen wastewater comprises ammonium carbonate, the pH value is adjusted to 13, then air stripping is carried out, the air stripping temperature is 25 ℃, the time is 1.5h, primary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 1.8 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and stripping are carried out by adopting steam, the stripping and stripping temperature is 100 ℃, the time is 0.2h, and secondary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 300 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 25 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.2MPa, the osmotic vaporization membrane is made of polyvinyl alcohol, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by hydrochloric acid during the osmotic deamination, the rest is processed ammonia nitrogen wastewater, and the ammonia nitrogen content of the processed ammonia nitrogen wastewater is reduced to 10 ppm.
According to the invention, through the combined deamination treatment process, the deamination rate of the ammonia nitrogen wastewater is high and can reach 99.96%; the method has low cost and no secondary pollution.
Example 5:
the embodiment provides a method for ammonia nitrogen wastewater deamination treatment, which comprises the following steps:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the source of the ammonia nitrogen wastewater to be treated is ammonia-containing waste gas treatment absorption liquid, the ammonia nitrogen content of the ammonia nitrogen wastewater is 75g/L, the ammonia nitrogen wastewater comprises ammonium chloride, the pH value is adjusted to 11, then air stripping is carried out, the air stripping temperature is 40 ℃, the time is 1.25h, primary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 3.6 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and air stripping is carried out by adopting steam, the stripping and air stripping temperature is 90 ℃, the time is 0.4h, and secondary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 500 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 35 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.4MPa, the osmotic vaporization membrane is made of polyvinyl chloride, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by hydrochloric acid during the osmotic deamination, the rest is processed ammonia nitrogen wastewater, and the ammonia nitrogen content in the processed ammonia nitrogen wastewater is reduced to 9 ppm.
According to the invention, by the combined deamination treatment process, the deamination rate of the ammonia nitrogen wastewater is high and can reach 99.99%; the method has low cost and no secondary pollution.
The method adopts a combined process to carry out deamination treatment according to the composition of the ammonia nitrogen wastewater, and the combined process sequentially adopts air stripping, steam stripping and osmotic deamination methods, so that the ammonia nitrogen in the wastewater can adopt proper treatment processes at different concentrations to realize higher ammonia nitrogen removal rate which can reach more than 99.9%; the method is simple to operate, low in cost, suitable for treating various types of wastewater containing ammonia nitrogen, large in treatment capacity and free of secondary pollution.
The present invention is illustrated by the above-described embodiments of the detailed apparatus and method of the present invention, but the present invention is not limited to the above-described detailed apparatus and method, i.e., it is not intended that the present invention be implemented by relying on the above-described detailed apparatus and method. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the means for substitution and addition of means for carrying out the invention, selection of specific means, etc., are within the scope and disclosure of the invention.
Claims (10)
1. The ammonia nitrogen wastewater deamination treatment method is characterized by comprising the following steps:
(1) adjusting the pH of the ammonia nitrogen wastewater to be treated, and then carrying out air stripping to obtain primary ammonia nitrogen wastewater;
(2) carrying out steam stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1) to obtain secondary ammonia nitrogen wastewater;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2) to obtain treated ammonia nitrogen wastewater.
2. The method according to claim 1, wherein the source of the ammonia nitrogen wastewater to be treated in step (1) comprises any one or a combination of at least two of landfill leachate, ammonia-containing waste gas treatment absorption liquid or ammonium-containing waste liquid generated in smelting;
preferably, the ammonia nitrogen content in the ammonia nitrogen wastewater to be treated in the step (1) is 10-100 g/L;
preferably, the composition of the ammonia nitrogen wastewater to be treated in the step (1) comprises any one or a combination of at least two of ammonium sulfate, ammonium carbonate or ammonium chloride.
3. The method according to claim 1 or 2, wherein the pH value is adjusted to 10-14 in the step (1);
preferably, the air stripping in the step (1) is air circulation stripping;
preferably, the temperature of the air stripping in the step (1) is 20-50 ℃;
preferably, the air stripping time in the step (1) is 0.5-2 h.
4. The method according to any one of claims 1 to 3, wherein the ammonia blown off by the air in the step (1) is absorbed by water, and the ammonia water is recovered;
preferably, the ammonia nitrogen content of the primary ammonia nitrogen wastewater in the step (1) is 1-5 g/L.
5. The process according to any one of claims 1 to 4, wherein the stripping in step (2) is stripping with steam;
preferably, the temperature of the stripping and stripping in the step (2) is 85-105 ℃;
preferably, the stripping and stripping time in the step (2) is 0.1-0.5 h.
6. The method according to any one of claims 1 to 5, wherein the steam and the ammonia carried out after the stripping in the step (2) are subjected to heat exchange with the air used for the stripping in the step (1) and then absorbed by water;
preferably, the ammonia nitrogen content of the secondary ammonia nitrogen wastewater in the step (2) is 200-800 ppm.
7. The method of any one of claims 1-6, wherein the osmotic deamination of step (3) is treated with a pervaporation membrane;
preferably, the temperature of the osmotic deamination in the step (3) is 20-40 ℃;
preferably, the pressure difference between two sides of the pervaporation membrane during the pervaporation is 0.1-0.5 MPa.
8. The method of claim 7, wherein the pervaporation membrane is made of any one of ceramic, polyvinyl chloride, and polyvinyl alcohol;
preferably, during the osmotic deamination, ammonia molecules pass through the pervaporation membrane to enter the other side, and are absorbed by the acid solution to maintain the pressure difference between the two sides of the pervaporation membrane.
9. The method according to any one of claims 1 to 8, characterized in that the ammonia nitrogen content in the ammonia nitrogen wastewater after the treatment in the step (3) is reduced to below 15 ppm;
preferably, the composition of the ammonia nitrogen wastewater treated in the step (3) comprises sodium sulfate and/or sodium chloride.
10. A method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(1) adjusting the pH value of ammonia nitrogen wastewater to be treated, wherein the ammonia nitrogen content of the ammonia nitrogen wastewater to be treated is 10-100 g/L, the ammonia nitrogen wastewater comprises any one or the combination of at least two of ammonium sulfate, ammonium carbonate or ammonium chloride, the pH value is adjusted to 10-14, then air stripping is carried out, the air stripping temperature is 20-50 ℃, the time is 0.5-2 h, primary ammonia nitrogen wastewater is obtained, and the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 1-5 g/L; absorbing the ammonia blown out by the air with water, and recovering to obtain ammonia water;
(2) carrying out stripping and air stripping on the primary ammonia nitrogen wastewater obtained in the step (1), wherein the stripping and air stripping is carried out by adopting steam, the stripping and air stripping temperature is 85-105 ℃, and the time is 0.1-0.5 h, so as to obtain secondary ammonia nitrogen wastewater, and the ammonia nitrogen content of the secondary ammonia nitrogen wastewater is 200-800 ppm; the steam after stripping and the ammonia brought out exchange heat with the air used in the stripping in the step (1) and are absorbed by water;
(3) and (3) performing osmotic deamination on the secondary ammonia nitrogen wastewater obtained in the step (2), wherein the osmotic deamination is processed by adopting an osmotic vaporization membrane, the temperature of the osmotic deamination is 20-40 ℃, the pressure difference between two sides of the osmotic vaporization membrane is 0.1-0.5 MPa, the material of the osmotic vaporization membrane comprises any one of ceramics, polyvinyl chloride or polyvinyl alcohol, ammonia molecules pass through the osmotic vaporization membrane and enter the other side of the osmotic vaporization membrane to be absorbed by acid liquor during the osmotic deamination, the pressure difference between two sides of the osmotic vaporization membrane is maintained, the rest is the processed ammonia nitrogen wastewater, and the ammonia nitrogen content of the processed ammonia nitrogen wastewater is reduced to below 15 ppm.
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| CN202210201567.XA CN114477558A (en) | 2022-03-03 | 2022-03-03 | Ammonia-removing treatment method for ammonia nitrogen wastewater |
| PCT/CN2022/092512 WO2023165020A1 (en) | 2022-03-03 | 2022-05-12 | Method for deamination treatment of ammonia-nitrogen wastewater |
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