CN109126770B - Method and device for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater - Google Patents
Method and device for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater Download PDFInfo
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- CN109126770B CN109126770B CN201710501036.1A CN201710501036A CN109126770B CN 109126770 B CN109126770 B CN 109126770B CN 201710501036 A CN201710501036 A CN 201710501036A CN 109126770 B CN109126770 B CN 109126770B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 238000005097 cold rolling Methods 0.000 title claims abstract description 46
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 89
- 235000012211 aluminium silicate Nutrition 0.000 claims description 89
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 89
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 57
- 239000000571 coke Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 25
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 238000012856 packing Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000007725 thermal activation Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 16
- 239000010959 steel Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/613—
-
- B01J35/617—
-
- B01J35/647—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention belongs to the technical field of water treatment, and provides a method and a device for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolled high-salinity wastewater. The cold rolling water quality after the treatment by the method is characterized in that: the Total Dissolved Solids (TDS) is 4500-7200 mg/L, WSOC is 3-6 mg/L, and ammonia nitrogen is 0.3-1.1 mg/L. By adopting the technical scheme of the method, the treatment effect is stable, and the production and operation cost is low. The invention belongs to an environment-friendly steel green production system.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a technical scheme for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolled high-salinity wastewater.
Background
The steel industry is a high-energy-consumption, high-resource and high-pollution industry, and the water resource consumption of the steel industry is huge and accounts for about 14 percent of the water consumption of the national industry.
The national development and improvement committee of 7 months in 2005 issued "iron and steel industry development policy", put forward higher targets and more specific requirements for the development of circular economy, energy and resource conservation and sustainable development road of the iron and steel industry, and under the condition of global resource shortage, low energy consumption, low pollution and low emission become the needs of social development.
The unit water consumption of the steel enterprises in China is still higher than the level of the advanced steel enterprises in China, so that the new water consumption per ton of steel of the steel enterprises is reduced, the water recycling rate of the steel enterprises is improved, and the comprehensive treatment and recycling of the wastewater of the steel enterprises are enhanced, which is one of the keys for realizing the sustainable development of the steel enterprises in China.
Iron and steel enterprises can generate a large amount of high-salinity wastewater in the cold rolling wastewater process. Mainly generated in the advanced treatment processes of ultrafiltration, nanofiltration and reverse osmosis of wastewater. Water quality analysis shows that the cold-rolled thin oil reverse osmosis strong brine is typical industrial wastewater with high salt content, high water-soluble organic carbon and ammonia nitrogen.
To date, there has been no targeted treatment method and process. The invention aims to develop an economic and efficient pollutant treatment process according to the water quality and quantity condition of the cold rolling thin oil reverse osmosis concentrated water, takes the cyclic utilization, energy conservation and emission reduction as main tasks, reduces the environmental pollution and actively deals with increasingly strict environmental protection regulations. The water-soluble organic carbon is water-soluble organic carbon, abbreviated as WSOC.
So far, no treatment method and process aiming at water-soluble organic carbon and ammonia nitrogen in cold rolling high-salinity wastewater exist. The invention aims to develop an economic and efficient pollutant treatment process according to the water quality and water quantity condition of cold rolling high-salinity wastewater, takes the cyclic utilization, energy conservation and emission reduction as main tasks, reduces environmental pollution, and actively deals with increasingly strict environmental protection regulations.
Disclosure of Invention
In order to solve the problems, the invention provides a technical scheme for completely removing water-soluble organic carbon and ammonia nitrogen in cold rolling high-salinity wastewater for the first time, and belongs to an environment-friendly steel production process system.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the method for simultaneously removing the water-soluble organic carbon and ammonia nitrogen in the cold-rolling high-salinity wastewater is characterized by comprising the following steps of:
(1) ozone generated by an ozone generator enters the high-efficiency reaction tower through a pipeline through an air inlet, cold-rolled high-salinity wastewater enters the high-efficiency reaction tower from the bottom of the high-efficiency reaction tower, a bottom filler layer is arranged at the lower part of the high-efficiency reaction tower, and a kaolin loaded iron-nickel catalyst is placed in the high-efficiency reaction tower;
the kaolin loaded iron-nickel catalyst is prepared by the following steps: 1) screening of kaolin: the kaolin mainly comprises alumina and silicon dioxide, wherein the mass percent of the alumina is 32-46%, the mass percent of the silicon dioxide is 41-53%, and impurities such as ferric oxide, calcium oxide and the like in the kaolin are all lower than 1%; selecting a molecular sieve of 80-100 meshes, and selecting the screened kaolin; 2) acidification of kaolin: mixing kaolin according to a solid-to-liquid ratio of 1: 3-6 percent of the mixture is put into a 3-7 percent dilute hydrochloric acid solution, mechanically stirred for 100-220 minutes at a constant temperature of 55-65 ℃, centrifugally separated after stirring, washed for 3 times by distilled water, and mixed according to a solid-to-liquid ratio of 1: 2-4 percent of the kaolin is put into a 1-2 percent dilute sulfuric acid solution, mechanically stirred for 150-260 minutes at a constant temperature of 75-80 ℃, then centrifugally separated, washed to be neutral by distilled water, and the acidified kaolin is placed in a 105-125 ℃ forced air drying oven to be dried for 3-4 hours and cooled for later use; 3) thermal activation of kaolin: putting the cooled high kaolin into a muffle furnace, heating to 750 ℃ at a speed of 5-10 ℃/min, keeping the temperature at 750 ℃ for 45-95 min, and then naturally cooling; 4) preparing a solution: preparing an iron nitrate solution with the concentration of 16-32% calculated by metal elements, adding 50-80 mg/L nickel sulfate into the mixed solution, and then stirring at the speed of 75-95 r/min for 3-4 hours to form an impregnation solution; 5) carrier impregnation: soaking the kaolin carrier in the soaking solution in a thermostat at 55 ℃ for 8-12 hours; then taking out the kaolin carrier, and airing at room temperature; 6) and (3) high-temperature sintering: placing kaolin in a high-temperature furnace, taking nitrogen as protective gas, heating to 430-450 ℃ at a speed of 5 ℃/min, roasting at constant temperature for 70-125 min, heating to 620-670 ℃ at a speed of 10 ℃/min, roasting at constant temperature for 65-155 min, and naturally cooling to obtain the kaolin loaded ironA nickel catalyst with a BET specific surface area of 24.5-27.8 m2(ii)/g, the average pore diameter is 2.3-3.8 nm;
(2) then, cold rolling high-salinity wastewater enters a top packing layer through a middle water layer, the middle water layer accounts for 5-10% of the volume of the whole reaction tower, and an active coke-loaded manganese-based catalyst is placed in a top catalyst layer;
(3) and finally, discharging cold rolling high-salinity wastewater through a water outlet at the top, discharging tail gas such as ozone through an exhaust port, and placing a high-temperature ozone quencher in the exhaust port at the temperature of 200-230 ℃ to ensure that safe gas is discharged.
Further, the active coke-loaded manganese-based catalyst is prepared by the following steps: 1) and (3) selecting the coal-based active coke: selecting the material with the granularity of 10-15 meshes and the specific surface area of 235-321 m2Active coke per gram; 2) preparing a solution: preparing a manganese nitrate solution with the concentration of 7-12% by calculating metal elements to form an impregnation solution; 3) carrier impregnation: immersing the granular active coke into the impregnation solution according to the solid-to-liquid ratio of 1: 3-5, and impregnating for 450-870 min at 55-75 ℃; then taking out the activated carbon carrier, and airing at room temperature; 4) and (3) high-temperature sintering: drying the active coke carrier in a blast heating box at 125 ℃ for 3 hours, cooling, putting the active coke carrier into a muffle furnace, heating to 370-510 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 80-160 min, and naturally cooling to obtain the active coke-loaded manganese-based catalyst with the specific surface area of 561-674 m2/g。
Further, the kaolin loaded iron-nickel catalyst accounts for 55-65% of the total volume.
Further, the top packing layer accounts for 35-45% of the total volume.
According to the method for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolled high-salinity wastewater, the air quantity of an ozone air inlet is 565-1289 Nm3The ozone output is 76-145 kg/h, and the ozone concentration is 7.5-10.2 wt%.
According to the method for simultaneously removing the water-soluble organic carbon and the ammonia nitrogen in the cold-rolling high-salinity wastewater, the water quality characteristics of the cold-rolling high-salinity wastewater before treatment are as follows: the Total Dissolved Solids (TDS) is 4500-7200 mg/L, WSOC is 11-35 mg/L, and ammonia nitrogen is 6-11 mg/L.
According to the method for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater, the cold-rolling water quality is characterized by comprising the following steps: the Total Dissolved Solids (TDS) is 4500-7200 mg/L, WSOC is 3-6 mg/L, and ammonia nitrogen is 0.3-1.1 mg/L.
The invention also provides a device applying the method for simultaneously removing the water-soluble organic carbon and the ammonia nitrogen in the cold-rolled high-salinity wastewater, which comprises a high-efficiency reaction tower, wherein an ozone inlet 1 and a water inlet 3 are respectively arranged at two sides of the bottom of the high-efficiency reaction tower, and an ozone inlet multipoint distributor 2 is arranged above the ozone inlet 1; the tower body of the high-efficiency reaction tower is respectively a bottom packing layer 4, a middle water layer 6 and a top packing layer 7 from bottom to top, the upper part of the high-efficiency reaction tower is provided with a water outlet 9, the top end of the high-efficiency reaction tower is provided with an air outlet 10, and the air outlet 10 is provided with an ozone quencher 11.
Further, a kaolin loaded iron-nickel catalyst 5 is arranged in the bottom packing layer 4, and accounts for 55-65% of the total volume; an active coke loaded manganese-based catalyst 8 is arranged in the top packing layer 7, and the top packing layer accounts for 35-45% of the total volume.
Detailed description of the invention:
a high-efficiency reaction tower treatment system for removing water-soluble organic carbon and ammonia nitrogen in cold-rolled high-salinity wastewater comprises an ozone air inlet, an ozone air inlet multipoint distributor, a water inlet, a bottom packing layer, a kaolin loaded iron-nickel catalyst, a middle water layer, a top packing layer, an active coke loaded manganese-based catalyst, a water outlet, an air outlet and an ozone quencher.
The water quality characteristics of the cold rolling high-salinity wastewater are as follows: the Total Dissolved Solids (TDS) is 4500-7200 mg/L, WSOC is 11-35 mg/L, and ammonia nitrogen is 6-11 mg/L.
Ozone generated by the ozone generator enters the efficient reaction tower through the air inlet through the pipeline, and the air quantity of the ozone air inlet is 565-1289 Nm3The ozone output is 76-145 kg/h, and the ozone concentration is 7.5-10.2 wt%. Ozone enters the high-efficiency reaction tower through the ozone inlet multipoint distributor. The multi-point distributor feeds the ozone into the bottom and middle water layer of the reaction tower, so that the ozone in the whole reaction tower can be concentratedThe degree remains substantially uniform.
Cold-rolled high-salinity wastewater enters the efficient reaction tower from the bottom, the lower end of the efficient reaction tower is provided with a bottom filler layer, and a kaolin loaded iron-nickel catalyst is placed in the bottom filler layer and accounts for 55-65% of the total volume. The kaolin loaded iron-nickel catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of the kaolin loaded iron-nickel catalyst: 1) screening of kaolin: the kaolin mainly comprises alumina and silicon dioxide, wherein the mass percent of the alumina is 32-46%, the mass percent of the silicon dioxide is 41-53%, and impurities such as ferric oxide, calcium oxide and the like in the kaolin are all lower than 1%. Selecting a molecular sieve of 80-100 meshes, and selecting the screened kaolin. 2) Acidification of kaolin: mixing kaolin according to a solid-to-liquid ratio of 1: 3-6 percent of the mixture is put into a 3-7 percent dilute hydrochloric acid solution, mechanically stirred for 100-220 minutes at a constant temperature of 55-65 ℃, centrifugally separated after stirring, washed for 3 times by distilled water, and mixed according to a solid-to-liquid ratio of 1: 2-4 percent of the kaolin is put into a 1-2 percent dilute sulfuric acid solution, mechanically stirred for 150-260 minutes at a constant temperature of 75-80 ℃, then centrifugally separated, washed to be neutral by distilled water, and the acidified kaolin is placed in a 105-125 ℃ forced air drying oven to be dried for 3-4 hours and cooled for later use. 3) Thermal activation of kaolin: and (3) putting the cooled high kaolin into a muffle furnace, heating to 750 ℃ at a speed of 5-10 ℃/min, keeping the temperature at 750 ℃ for 45-95 min, and then naturally cooling. 4) Preparing a solution: preparing an iron nitrate solution with the concentration of 16-32% (calculated by metal elements), adding 50-80 mg/L nickel sulfate into the mixed solution, and stirring at the speed of 75-95 r/min for 3-4 hours to form an impregnation solution. 5) Carrier impregnation: soaking the kaolin carrier in the soaking solution in a thermostat at 55 ℃ for 8-12 hours; the kaolin support was then removed and allowed to air dry at room temperature. 6) And (3) high-temperature sintering: placing kaolin in a high-temperature furnace, taking nitrogen as protective gas, heating to 430-450 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 70-125 min, heating to 620-670 ℃ at a speed of 10 ℃/min, roasting at a constant temperature for 65-155 min, and naturally cooling to obtain the kaolin-loaded iron-nickel catalyst, wherein the BET specific surface area is 24.5-27.8 m2(ii)/g, the average pore diameter is 2.3 to 3.8 nm. Kaolin anionThe iron-nickel-loaded catalyst can simultaneously remove soluble organic carbon and ammonia nitrogen in the cold-rolled high-salinity wastewater, the catalyst decomposes ozone into active groups, the active groups can convert the solubility into carbon dioxide and micromolecular organic matters, and the ammonia nitrogen is oxidized into nitrogen.
Then the cold rolling high-salinity wastewater enters the top packing layer through the middle water layer. The volume of the middle water layer accounts for 5-10% of the volume of the whole reaction tower. The function of the middle water layer is to play a role of buffering and separate different catalyst fillers from each other.
The top packing layer accounts for 35-45% of the total volume, and the middle catalyst layer is filled with an active coke-loaded manganese-based catalyst. The active coke-loaded manganese-based catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of active coke-loaded manganese-based catalyst: 1) and (3) selecting the coal-based active coke: selecting the material with the granularity of 10-15 meshes and the specific surface area of 235-321 m2Active coke per gram. 2) Preparing a solution: preparing a manganese nitrate solution with the concentration of 7-12% (calculated by metal elements) to form an impregnation solution 3) impregnating the carrier: immersing the granular active coke into the impregnation solution according to the solid-to-liquid ratio of 1: 3-5, and impregnating for 450-870 min at 55-75 ℃; then taking out the activated carbon carrier, and airing at room temperature. 4) And (3) high-temperature sintering: drying the active coke carrier in a blast heating box at 125 ℃ for 3 hours, cooling, putting the active coke carrier into a muffle furnace, heating to 370-510 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 80-160 min, and naturally cooling to obtain the active coke-loaded manganese-based catalyst with the specific surface area of 561-674 m2(ii) in terms of/g. The active coke-loaded manganese-based catalyst is specially developed for cold rolling high-salinity wastewater, can catalyze and oxidize soluble organic carbon and ammonia nitrogen, and can adsorb partial soluble organic matters.
And then discharging cold rolling high-salinity wastewater through a water outlet at the top, discharging tail gas such as ozone and the like through an exhaust port, and placing a high-temperature ozone quencher in the exhaust port at the temperature of 200-230 ℃ to ensure that safe gas is discharged.
Advantageous technical effects
The invention discloses a technology for removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater. The cold rolling water quality characteristics after treatment are as follows: the Total Dissolved Solids (TDS) is 4500-7200 mg/L, WSOC is 3-6 mg/L, and ammonia nitrogen is 0.3-1.1 mg/L. By adopting the technical scheme of the method, the treatment effect is stable, and the production and operation cost is low. The invention belongs to an environment-friendly steel green production system.
Drawings
FIG. 1 is a high-efficiency reaction tower treatment system for removing water-soluble organic carbon and ammonia nitrogen in cold-rolled high-salinity wastewater.
Wherein: the ozone gas inlet device comprises an ozone gas inlet 1, an ozone gas inlet multipoint distributor 2, a water inlet 3, a bottom filler layer 4, a kaolin loaded iron-nickel catalyst 5, a middle water layer 6, a top filler layer 7, an active coke loaded manganese-based catalyst 8, a water outlet 9, an exhaust port 10 and an ozone quencher 11.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
the water quality characteristics of the cold rolling high-salinity wastewater are as follows: total Dissolved Solids (TDS) was 6520mg/L, WSOC was 32mg/L, and ammonia nitrogen was 10 mg/L.
Ozone generated by the ozone generator enters the high-efficiency reaction tower through a pipeline through an air inlet, and the air quantity of the ozone inlet is 51107Nm3The ozone production was 121kg/h and the ozone concentration was 9.7 wt.%. Ozone enters the high-efficiency reaction tower through the ozone inlet multipoint distributor. The multi-point distributor feeds ozone into the bottom and middle water layers of the reaction tower, so that the ozone concentration of the whole reaction tower can be kept basically consistent.
Cold-rolled high-salinity wastewater enters the high-efficiency reaction tower from the bottom, the lower end of the high-efficiency reaction tower is provided with a bottom filler layer, and a kaolin loaded iron-nickel catalyst is placed in the high-efficiency reaction tower and accounts for 55% of the total volume. The kaolin loaded iron-nickel catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of the kaolin loaded iron-nickel catalyst: 1) screening of kaolin: the kaolin mainly comprises alumina and silicon dioxide, wherein the mass percent of the alumina is 42 percent, the mass percent of the silicon dioxide is 45 percent, and the kaolin contains the alumina and the silicon dioxideThe impurities such as ferric oxide, calcium oxide and the like are all less than 1 percent. Selecting 100-mesh molecular sieve, and selecting the kaolin after sieving. 2) Acidification of kaolin: mixing kaolin according to a solid-to-liquid ratio of 1: 4, mechanically stirring at the constant temperature of 65 ℃ for 190 minutes, performing centrifugal separation after stirring, cleaning for 3 times by using distilled water, and then adding the mixture into a 5% dilute hydrochloric acid solution according to the solid-liquid ratio of 1: 4, mechanically stirring at the constant temperature of 78 ℃ for 235 minutes, then centrifugally separating, washing with distilled water to be neutral, placing the acidified kaolin in a blast drying oven at the temperature of 115 ℃ for drying for 4 hours, and cooling for later use. 3) Thermal activation of kaolin: and (3) putting the cooled kaolin into a muffle furnace, heating to 750 ℃ at a speed of 10 ℃/min, keeping the temperature of 750 ℃ for 85min, and then naturally cooling. 4) Preparing a solution: an iron nitrate solution having a solution concentration of 27% (in terms of metal element) was prepared, 76mg/L of nickel sulfate was added to the mixed solution, and then stirred at 90 rpm for 4 hours to form an impregnation solution. 5) Carrier impregnation: soaking the kaolin carrier in the soaking solution in a thermostat at 55 ℃ for 11 hours; the kaolin support was then removed and allowed to air dry at room temperature. 6) And (3) high-temperature sintering: placing kaolin in a high-temperature furnace, taking nitrogen as protective gas, heating to 450 ℃ at a speed of 5 ℃/min, roasting at constant temperature for 115min, heating to 655 ℃ at a speed of 10 ℃/min, roasting at constant temperature for 145min, and naturally cooling to obtain the kaolin-loaded iron-nickel catalyst with a BET specific surface area of 26.5m2In terms of/g, the mean pore diameter is 3.7 nm. The kaolin loaded iron-nickel catalyst can simultaneously remove soluble organic carbon and ammonia nitrogen in cold rolling high-salinity wastewater, the catalyst decomposes ozone into active groups, the active groups can convert the solubility into carbon dioxide and micromolecular organic matters, and the ammonia nitrogen is oxidized into nitrogen.
Then the cold rolling high-salinity wastewater enters the top packing layer through the middle water layer. The intermediate water layer accounts for 10% of the volume of the whole reaction tower. The function of the middle water layer is to play a role of buffering and separate different catalyst fillers from each other.
The top packing layer accounts for 35 percent of the total volume, and the middle catalytic layer is internally provided with an active coke loaded manganese-based catalyst. The active coke-loaded manganese-based catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of active coke-loaded manganese-based catalyst: 1) and (3) selecting the coal-based active coke: selecting the material with the grain size of 15 meshes and the specific surface area of 311m2Active coke per gram. 2) Preparing a solution: preparing a manganese nitrate solution with the concentration of 11% (calculated by metal elements) to form an impregnation solution 3) impregnating the carrier: immersing the granular active coke into the impregnation solution according to the solid-to-liquid ratio of 1: 3-5, and impregnating for 650min at 70 ℃; then taking out the activated carbon carrier, and airing at room temperature. 4) And (3) high-temperature sintering: drying the active coke carrier in a blast heating box at 125 ℃ for 3 hours, cooling, putting the active coke carrier into a muffle furnace, heating to 480 ℃ at the speed of 5 ℃/min, roasting at constant temperature for 145min, and naturally cooling to obtain the active coke-loaded manganese-based catalyst with the specific surface area of 652m2(ii) in terms of/g. The active coke-loaded manganese-based catalyst is specially developed for cold rolling high-salinity wastewater, can catalyze and oxidize soluble organic carbon and ammonia nitrogen, and can adsorb partial soluble organic matters.
Then the cold rolling high salinity wastewater is discharged through a water outlet at the top, tail gas such as ozone is discharged through an exhaust port, a high-temperature ozone quencher is arranged in the exhaust port, the temperature is 220 ℃, and safe gas discharge is ensured.
The cold rolling water quality characteristics after treatment are as follows: total Dissolved Solids (TDS) was 6570mg/L, WSOC was 4mg/L, and ammonia nitrogen was 0.9 mg/L.
Example 2:
the water quality characteristics of the cold rolling high-salinity wastewater are as follows: the Total Dissolved Solids (TDS) was 5320mg/L, WSOC was 21mg/L, and ammonia nitrogen was 8 mg/L.
Ozone generated by the ozone generator enters the high-efficiency reaction tower through a pipeline through an air inlet, and the air quantity of the ozone air inlet is 765Nm3The ozone production was 89kg/h and the ozone concentration was 8.7 wt.%. Ozone enters the high-efficiency reaction tower through the ozone inlet multipoint distributor. The multi-point distributor feeds ozone into the bottom and middle water layers of the reaction tower, so that the ozone concentration of the whole reaction tower can be kept basically consistent.
Cold-rolled high-salinity wastewater enters the high-efficiency reaction tower from the bottom, the lower end of the high-efficiency reaction tower is provided with a bottom filler layer, and a kaolin loaded iron-nickel catalyst is placed in the high-efficiency reaction tower and accounts for 60 percent of the total volume. The kaolin loaded iron-nickel catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of the kaolin loaded iron-nickel catalyst: 1) screening of kaolin: the main components of the kaolin are alumina and silicon dioxide, wherein the mass percent of the alumina is 37 percent, the mass percent of the silicon dioxide is 48 percent, and the impurities such as ferric oxide, calcium oxide and the like in the kaolin are all lower than 1 percent. Selecting a 80-mesh molecular sieve, and selecting kaolin sieved by the 80-mesh molecular sieve. 2) Acidification of kaolin: mixing kaolin according to a solid-to-liquid ratio of 1:3, mechanically stirring at a constant temperature of 60 ℃ for 150 minutes, performing centrifugal separation after stirring, cleaning for 3 times by using distilled water, and then performing solid-liquid ratio of 1: 2, mechanically stirring for 190 minutes at a constant temperature of 75 ℃, then centrifugally separating, washing to be neutral by using distilled water, placing the acidified kaolin in a blast drying oven at 115 ℃ for drying for 3 hours, and cooling for later use. 3) Thermal activation of kaolin: and (3) putting the cooled high kaolin into a muffle furnace, heating to 750 ℃ at a speed of 5 ℃/min, keeping the temperature of 750 ℃ for 60min, and then naturally cooling. 4) Preparing a solution: a solution of 19% (in terms of metal element) ferric nitrate was prepared, 61mg/L nickel sulfate was added to the mixed solution, and the mixture was stirred at 75 rpm for 3 hours to form an impregnation solution. 5) Carrier impregnation: soaking the kaolin carrier in the soaking solution in a thermostat at 55 ℃ for 9 hours; the kaolin support was then removed and allowed to air dry at room temperature. 6) And (3) high-temperature sintering: placing kaolin in a high-temperature furnace, taking nitrogen as protective gas, heating to 430 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 85min, heating to 640 ℃ at a speed of 10 ℃/min, roasting at a constant temperature for 85min, and naturally cooling to obtain the kaolin-loaded iron-nickel catalyst, wherein the BET specific surface area is 25.6m2In terms of/g, the mean pore diameter is 2.9 nm. The kaolin loaded iron-nickel catalyst can simultaneously remove soluble organic carbon and ammonia nitrogen in cold rolling high-salinity wastewater, the catalyst decomposes ozone into active groups, the active groups can convert the solubility into carbon dioxide and micromolecular organic matters, and the ammonia nitrogen is oxidized into nitrogen.
Then the cold rolling high-salinity wastewater enters the top packing layer through the middle water layer. The intermediate aqueous layer accounts for 5% of the volume of the whole reaction column. The function of the middle water layer is to play a role of buffering and separate different catalyst fillers from each other.
The top packing layer accounts for 35 percent of the total volume, and the middle catalytic layer is internally provided with an active coke loaded manganese-based catalyst. The active coke-loaded manganese-based catalyst is specially developed aiming at the characteristics of cold rolling high-salinity wastewater.
Preparation of active coke-loaded manganese-based catalyst: 1) and (3) selecting the coal-based active coke: selecting the particle size of 10 meshes and the specific surface area of 262m2Active coke per gram. 2) Preparing a solution: preparing a manganese nitrate solution with the concentration of 8% (calculated by metal elements) to form an impregnation solution 3) impregnating the carrier: immersing the granular active coke into an impregnation solution according to a solid-to-liquid ratio of 1: 3-5, and impregnating for 560min at 55 ℃; then taking out the activated carbon carrier, and airing at room temperature. 4) And (3) high-temperature sintering: drying the active coke carrier in a blast heating box at 125 ℃ for 3 hours, cooling, putting the active coke carrier into a muffle furnace, heating to 370-510 ℃ at the speed of 5 ℃/min, roasting at constant temperature for 95min, and naturally cooling to obtain the active coke-loaded manganese-based catalyst with the specific surface area of 598m2(ii) in terms of/g. The active coke-loaded manganese-based catalyst is specially developed for cold rolling high-salinity wastewater, can catalyze and oxidize soluble organic carbon and ammonia nitrogen, and can adsorb partial soluble organic matters.
Then the cold rolling high salinity wastewater is discharged through a water outlet at the top, tail gas such as ozone is discharged through an exhaust port, a high-temperature ozone quencher is arranged in the exhaust port, the temperature is 200 ℃, and safe gas discharge is ensured.
The cold rolling water quality characteristics after treatment are as follows: the Total Dissolved Solids (TDS) was 5360mg/L, WSOC 4mg/L, and Ammonia Nitrogen 0.6 mg/L.
In conclusion, the system for simultaneously cold rolling the water-soluble organic carbon and the ammonia nitrogen in the high-salinity wastewater has the advantages of low one-time investment, stable wastewater treatment effect and simple operation. The invention fully embodies the effects of energy conservation and emission reduction, and is an environment-friendly green steel production process.
Of course, those skilled in the art should recognize that the above-described embodiments are illustrative only, and not limiting, and that changes and modifications can be made within the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A method for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater is characterized by comprising the following steps:
(1) ozone generated by an ozone generator enters the high-efficiency reaction tower through a pipeline through an air inlet, cold-rolled high-salinity wastewater enters the high-efficiency reaction tower from the bottom of the high-efficiency reaction tower, a bottom filler layer is arranged at the lower part of the high-efficiency reaction tower, and a kaolin loaded iron-nickel catalyst is placed in the high-efficiency reaction tower; the kaolin loaded iron-nickel catalyst accounts for 55-65% of the total volume;
the kaolin loaded iron-nickel catalyst is prepared by the following steps: 1) screening of kaolin: the kaolin mainly comprises alumina and silicon dioxide, wherein the mass percent of the alumina is 32-46%, the mass percent of the silicon dioxide is 41-53%, and the impurities of ferric oxide and calcium oxide in the kaolin are lower than 1%; selecting a molecular sieve of 80-100 meshes, and selecting the screened kaolin; 2) acidification of kaolin: mixing kaolin according to a solid-to-liquid ratio of 1: 3-6 percent of the mixture is put into a 3-7 percent dilute hydrochloric acid solution, mechanically stirred for 100-220 minutes at a constant temperature of 55-65 ℃, centrifugally separated after stirring, washed for 3 times by distilled water, and mixed according to a solid-to-liquid ratio of 1: 2-4 percent of the kaolin is put into a 1-2 percent dilute sulfuric acid solution, mechanically stirred for 150-260 minutes at a constant temperature of 75-80 ℃, then centrifugally separated, washed to be neutral by distilled water, and the acidified kaolin is placed in a 105-125 ℃ forced air drying oven to be dried for 3-4 hours and cooled for later use; 3) thermal activation of kaolin: placing the cooled kaolin into a muffle furnace, heating to 750 ℃ at a speed of 5-10 ℃/min, keeping the temperature at 750 ℃ for 45-95 min, and then naturally cooling; 4) preparing a solution: preparing an iron nitrate solution with the concentration of 16-32% calculated by metal elements, adding 50-80 mg/L nickel sulfate into the mixed solution, and then stirring at the speed of 75-95 r/min for 3-4 hours to form an impregnation solution; 5) carrier impregnation: soaking the kaolin carrier in the soaking solution in a thermostat at 55 ℃ for 8-12 hours; then taking out the kaolin carrier, and airing at room temperature; 6) and (3) high-temperature sintering: placing kaolin in a high temperature furnaceIn a high-temperature furnace using nitrogen as protective gas, firstly heating to 430-450 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 70-125 min, then heating to 620-670 ℃ at a speed of 10 ℃/min, roasting at a constant temperature for 65-155 min, and then naturally cooling to prepare the kaolin loaded iron-nickel catalyst, wherein the BET specific surface area is 24.5-27.8 m2(ii)/g, the average pore diameter is 2.3-3.8 nm;
(2) then, cold rolling high-salinity wastewater enters a top packing layer through a middle water layer, the middle water layer accounts for 5-10% of the volume of the whole reaction tower, and an active coke-loaded manganese-based catalyst is placed in the top packing layer;
(3) finally, discharging the cold rolling high-salinity wastewater through a water outlet at the top, discharging ozone tail gas through an exhaust port, and placing a high-temperature ozone quencher in the exhaust port at the temperature of 200-230 ℃ to ensure that the gas is discharged safely;
the active coke-loaded manganese-based catalyst is prepared by the following steps: 1) and (3) selecting the coal-based active coke: selecting the material with the granularity of 10-15 meshes and the specific surface area of 235-321 m2Active coke per gram; 2) preparing a solution: preparing a manganese nitrate solution with the concentration of 7-12% by calculating metal elements to form an impregnation solution; 3) carrier impregnation: immersing the granular active coke into the impregnation solution according to the solid-to-liquid ratio of 1: 3-5, and impregnating for 450-870 min at 55-75 ℃; then taking out the activated carbon carrier, and airing at room temperature; 4) and (3) high-temperature sintering: drying the active coke carrier in a blast heating box at 125 ℃ for 3 hours, cooling, putting the active coke carrier into a muffle furnace, heating to 370-510 ℃ at a speed of 5 ℃/min, roasting at a constant temperature for 80-160 min, and naturally cooling to obtain the active coke-loaded manganese-based catalyst with the specific surface area of 561-674 m2/g。
2. The method for simultaneously removing water-soluble organic carbon and ammonia nitrogen in cold-rolling high-salinity wastewater as claimed in claim 1, wherein the air amount of the ozone inlet is 565-1289 Nm3The ozone output is 76-145 kg/h, and the ozone concentration is 7.5-10.2 wt%.
3. The method for simultaneously removing the water-soluble organic carbon and the ammonia nitrogen in the cold-rolled high-salinity wastewater according to claim 1, characterized in that the water quality characteristics of the cold-rolled high-salinity wastewater before treatment are as follows: the total dissolved solid TDS is 4500-7200 mg/L, the WSOC is 11-35 mg/L, and the ammonia nitrogen is 6-11 mg/L.
4. The method for simultaneously removing the water-soluble organic carbon and the ammonia nitrogen in the cold-rolling high-salinity wastewater according to claim 1, characterized in that the cold-rolling water quality after treatment is characterized in that: the total dissolved solid TDS is 4500-7200 mg/L, the WSOC is 3-6 mg/L, and the ammonia nitrogen is 0.3-1.1 mg/L.
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