CN113200597A - Method and device for one-step method ozone synergistic chlorine oxidation advanced treatment of nitrogen and chlorine in wastewater - Google Patents
Method and device for one-step method ozone synergistic chlorine oxidation advanced treatment of nitrogen and chlorine in wastewater Download PDFInfo
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000460 chlorine Substances 0.000 title claims abstract description 50
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 50
- 239000002351 wastewater Substances 0.000 title claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 title description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 73
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000005273 aeration Methods 0.000 claims abstract description 14
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 26
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000004155 Chlorine dioxide Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 3
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000005276 aerator Methods 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 13
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000006213 oxygenation reaction Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- ZALMZWWJQXBYQA-UHFFFAOYSA-N [N].[Cl] Chemical compound [N].[Cl] ZALMZWWJQXBYQA-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method and a device for deeply treating nitrogen and chlorine in wastewater by one-step method ozone and chlorine oxidation. Mainly solves the technical problems that residual chlorine oxidant and byproducts are easy to form secondary pollution and the like in the existing method for treating ammonia nitrogen wastewater. The technical scheme of the invention is as follows: comprises the following steps: 1) adding ammonia nitrogen wastewater to be treated and sodium hypochlorite into a mixer at the same time, mixing, and flowing into a reactor; 2) the ORP controller detects the oxidation-reduction potential value of the mixed liquid entering the reactor and adjusts the flow of sodium hypochlorite according to the displayed value; 3) when the mixed liquid reaches the designated liquid level, starting the hydrodynamic cavitation oxygen-increasing aerator and the ozone generator, and 4) when the oxidation-reduction potential value detected by the ORP controller reaches the designated value 930-970mv, finishing the treatment of the mixed liquid. The device comprises a reactor, a hydrodynamic cavitation oxygen aeration machine, a pipeline mixer, an ammonia nitrogen wastewater intake pump, an ozone generator, a sodium hypochlorite feeding pump, a sodium hypochlorite dissolver, an ORP controller, an ammonia nitrogen online analyzer and the like.
Description
Technical Field
The invention belongs to the technical field of nitrogen-containing sewage treatment methods and devices, and particularly relates to a method and a device for deeply treating nitrogen and chlorine in wastewater through one-step method ozone and chlorine oxidation.
Background
With the development of industrial and agricultural production and the improvement of the living standard of people, more and more nitrogen-containing compounds are discharged into water, and the water body is seriously polluted. From the recent environmental quality bulletin, the main pollutants in water in China are ammonia nitrogen and organic matters. The pollutants further aggravate the contradiction of water resource shortage in China and seriously restrict the implementation of the strategy of sustainable development. Particularly, the discharge amount of nitrogen-containing compounds is rapidly increased, thereby not only causing eutrophication of water bodies, but also causing the outbreak of algae and the deterioration of water quality, increasing the difficulty and the cost of water treatment, even generating toxic action on people and organisms and influencing the normal survival and development of human beings and other organisms.
Along with the improvement of the environmental protection consciousness of people, the treatment standard of discharged sewage is also continuously improved. Various attempts and researches are made on the nitrogen-containing sewage treatment technology. The deep denitrification technology developed so far can be basically divided into a physical chemical method and a biological method, and the main principle of biological denitrification is to oxidize ammonia nitrogen in water into nitrogen and discharge the nitrogen out of a system through nitrification and denitrification treatment. It has the defects of large investment, complex operation and treatment effect influenced by natural conditions. The physical and chemical method is a chlorination method (also called breakpoint chlorination method), i.e. chlorine dioxide, chlorine, hypochlorite and other chlorine-containing oxidants are added into the ammonia nitrogen sewage to oxidize the ammonia nitrogen in the sewage into nitrogen and discharge the nitrogen out of the system. Has the advantages of high denitrification efficiency, less investment, no influence of environmental and climatic conditions, high reaction rate, disinfection effect and more research and application.
However, the method has the defects that the control operation difficulty of the dosage is high due to the continuous fluctuation of the content of ammonia nitrogen in the water to be treated; residual oxychlorination agent in the treated water, chloramine as a byproduct, chlorinated organic matters and the like are easy to cause secondary pollution, a dechlorination process is required to be added before the treated water is discharged, and the defects limit the practical application of chlorination denitrification.
Disclosure of Invention
The invention aims to solve the problems and provides a method and a device for deeply treating nitrogen and chlorine in wastewater by using a one-step method of ozone and chlorine oxidation.
In order to solve the technical problems, the invention adopts the technical scheme that:
the one-step method for deeply treating nitrogen and chlorine in wastewater by ozone and chlorine oxidation, which comprises the following steps:
1) adding ammonia nitrogen wastewater to be treated and sodium hypochlorite into a pipeline mixer at the same time, fully mixing to form a mixed solution, and flowing into a reactor; the weight ratio of the effective chlorine addition amount of the sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated is 7.6-8: 1;
2) the ORP controller detects the oxidation-reduction potential value of the mixed liquid entering the reactor in real time, and adjusts the flow of the sodium hypochlorite feeding pump in real time according to the display value detected by the ORP controller so as to control the dosage of the sodium hypochlorite; when the display value detected by the ORP controller reaches the range of 620-;
3) when the mixed liquid entering the reactor reaches the designated liquid level, closing the ammonia nitrogen wastewater inlet pump and the sodium hypochlorite feeding pump, and stopping the mixed liquid entering the reactor; starting the hydrodynamic cavitation oxygen aeration machine and the ozone generator, adjusting a flow meter of the ozone generator, adding the output ozone into the mixed liquid at a flow rate of 0.6-0.8 mg/min per liter of the mixed liquid, and fully reacting the ozone with ammonia nitrogen in a micron-sized bubble form under the hydrodynamic cavitation action to realize complete denitrification without residual chlorine; in the reaction process, the ORP controller detects the reaction degree of the mixed liquid in the reaction process in real time;
4) when the oxidation-reduction potential value detected by the ORP controller reaches the designated value of 930-970mv and is stabilized for five minutes and the display value of the ammonia nitrogen online analyzer reaches the designated value of 1mg/L or below, the mixed liquid in the reactor is treated completely, and the hydrodynamic cavitation oxygen aeration machine and the ozone generator are closed;
5) the drain valve of the reactor was opened to drain the treated mixed solution from the reactor.
Further, the sodium hypochlorite can be replaced by any one of chlorine, chlorine dioxide, calcium hypochlorite or dichloroisocyanuric acid.
The device for the method for deeply treating nitrogen and chlorine in wastewater by using one-step method of ozone in cooperation with oxychlorination comprises a reactor, a hydrodynamic cavitation oxygenation aerator, a pipeline mixer, an ammonia nitrogen wastewater inlet pump, an ozone generator, a sodium hypochlorite feeding pump, a sodium hypochlorite dissolver, a drain valve, an ORP controller and an ammonia nitrogen online analyzer, wherein the hydrodynamic cavitation oxygenation aerator is arranged in the reactor, an air inlet of the hydrodynamic cavitation oxygenation aerator is connected with an air outlet of the ozone generator, a water inlet of the ammonia nitrogen wastewater inlet pump is connected with a wastewater tank, a water outlet of the ammonia nitrogen wastewater inlet pump is connected with a wastewater inlet of the pipeline mixer, a water outlet of the pipeline mixer is connected with a water inlet of the reactor, a feed inlet of the feeding pump is connected with the sodium hypochlorite dissolver, a discharge outlet of the sodium hypochlorite feeding pump is connected with a feed inlet of the pipeline mixer, the ORP controller and the ammonia nitrogen online analyzer are arranged in the reactor, the ORP controller and the ammonia nitrogen online analyzer are used for detecting and controlling the addition amount and the reaction time of sodium hypochlorite respectively, and the drain valve is arranged at the bottom of one side of the reactor.
The invention has the beneficial effects that:
the invention adopts the quick reaction of hypochlorous acid and ammonia nitrogen in water to firstly generate monochloramine, the monochloramine has stable property and can exist in water for a long time, the stable property limits the continuous proceeding of the oxychlorination reaction, strong oxidant ozone is introduced into the water of the oxychlorination reaction system in a micro-bubble form through a hydrodynamic cavitation oxygenation aerator to efficiently react with intermediate reaction products in the water, the conversion reaction of the monochloramine to dichloramine is effectively promoted, the dichloramine is converted into nitrogen to escape from the water body, and the combined hypochlorous acid is released while the dichloramine is converted to continuously react with the monochloramine in the water, so the cycle is benign, the speed of the oxychlorination reaction is greatly promoted, the reaction degree is strengthened, and the aim of quick and thorough denitrification is achieved.
The invention has the advantages of complete denitrification, no harmful by-products, simple device, convenient operation and automatic control. The method for treating the chlorine system oxidant in the water body with the ammonia nitrogen exceeding the standard has low consumption, greatly reduces the consumption of the chlorine system oxidant, adapts to the environment with large water content and low temperature, can simultaneously reduce the chromaticity and COD index of the treated water body, comprehensively improves the water quality, and is suitable for popularization and application.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention;
FIG. 2 is a graph comparing the effect of the present invention on ammonia nitrogen removal with a conventional treatment method;
in fig. 1: the method comprises the following steps of 1-a reactor, 2-a hydrodynamic cavitation oxygenation aerator, 3-a pipeline mixer, 4-an ammonia nitrogen wastewater inlet pump, 5-an ozone generator, 6-a sodium hypochlorite feeding pump, 7-a sodium hypochlorite dissolver, 8-a drain valve, 9-an ORP controller and 10-an ammonia nitrogen online analyzer.
Detailed Description
The invention is further illustrated by the following figures and examples.
The method for deeply treating nitrogen and chlorine in wastewater by using one-step method ozone in cooperation with oxychlorination in the embodiment comprises the following steps of:
1) adding ammonia nitrogen wastewater to be treated and sodium hypochlorite into a pipeline mixer at the same time, fully mixing to form a mixed solution, and flowing into a reactor; the weight ratio of the effective chlorine addition amount of the sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated is 7.6: 1;
2) the ORP controller detects the oxidation-reduction potential value of the mixed liquid entering the reactor in real time, and adjusts the flow of the sodium hypochlorite feeding pump in real time according to the display value detected by the ORP controller so as to control the dosage of the sodium hypochlorite; when the display value detected by the ORP controller reaches the range of 620-;
3) when the mixed liquid entering the reactor reaches the designated liquid level, closing the ammonia nitrogen wastewater inlet pump and the sodium hypochlorite feeding pump, and stopping the mixed liquid entering the reactor; starting the hydrodynamic cavitation oxygen aeration machine and the ozone generator, adjusting a flow meter of the ozone generator, adding the output ozone into the mixed liquid at a flow rate of 0.6-0.8 mg/min per liter of the mixed liquid, and fully reacting the ozone with ammonia nitrogen in a micron-sized bubble form under the hydrodynamic cavitation action to realize complete denitrification without residual chlorine; in the reaction process, the ORP controller detects the reaction degree of the mixed liquid in the reaction process in real time;
4) when the oxidation-reduction potential value detected by the ORP controller reaches the designated value of 930-970mv and is stabilized for five minutes and the display value of an ammonia nitrogen online analyzer (salicylic acid method) reaches the designated value of 1mg/L or below, the mixed liquid in the reactor is treated completely, and the hydrodynamic cavitation oxygen-increasing aerator and the ozone generator are closed;
5) the drain valve of the reactor was opened to drain the treated mixed solution from the reactor.
The sodium hypochlorite can be replaced by any one of chlorine, chlorine dioxide, calcium hypochlorite or dichloroisocyanuric acid.
The weight ratio of the effective chlorine addition amount of the sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated can be randomly selected from 7.6-8: 1.
As shown in figure 1, the device for the one-step method ozone-assisted chlorine oxidation advanced treatment method of nitrogen and chlorine in wastewater comprises a reactor 1, a hydrodynamic cavitation aeration machine 2, a pipeline mixer 3, an ammonia nitrogen wastewater inlet pump 4, an ozone generator 5, a sodium hypochlorite feeding pump 6, a sodium hypochlorite dissolver 7, a drain valve 8, an ORP controller 9 and an ammonia nitrogen online analyzer (salicylic acid method) 10, wherein the hydrodynamic cavitation aeration machine 2 is arranged in the reactor 1, an air inlet of the hydrodynamic cavitation aeration machine 2 is connected with an air outlet of the ozone generator 5, an water inlet of the ammonia nitrogen wastewater inlet pump 4 is connected with a wastewater pool, an water outlet of the ammonia nitrogen wastewater inlet pump 4 is connected with a wastewater inlet of the pipeline mixer 3, a water outlet of the pipeline mixer 3 is connected with a water inlet of the reactor 1, a sodium hypochlorite feeding pump 6 is connected with a sodium hypochlorite feeding port dissolver 7, the discharge hole of the sodium hypochlorite feeding pump 6 is connected with the feed inlet of the pipeline mixer 3, the test heads of the ORP controller 9 and the ammonia nitrogen online analyzer 10 are arranged in the reactor 1, the ORP controller 9 and the ammonia nitrogen online analyzer 10 respectively detect and control the addition amount and the reaction time of the sodium hypochlorite, and the drain valve 8 is arranged at the bottom of one side of the reactor 1.
The method comprises the step of adding a sodium hypochlorite solution into a water body containing ammonia nitrogen to react to generate monochloramine, dichloramine and a small amount of trichloroamine. Partial chloramine continuously reacts along with the improvement of the chlorine-nitrogen ratio to finally generate nitrogen to escape from the water body, so that the aim of denitrification of the water body is fulfilled. The relevant reaction mechanism can be expressed by the following equation:
NaClO+H2O→HClO+NaOH ①
NH3+HClO→NH2Cl+H2O ②
NH2Cl+HClO→NHCl2+H2O ③
NHCl2+H2O→NOH+2Cl-+2H+ ④
NHCl2+NOH→N2↑+HClO+H++Cl- ⑤
the overall reaction formula is:
2NH3+3HClO→N2↑+3H2O+3NaCl ⑥
experimental research proves that the chlorine oxidation reaction of the nitrogen-containing water body has high reaction speed under the conditions of near-neutral pH value and normal environmental temperature. The main reaction can be basically completed within one minute, and the ammonia nitrogen is mainly generated into an intermediate product monochloramine through a reaction formula II under the condition that the mass ratio of the effective chlorine of the reaction sodium hypochlorite to the ammonia nitrogen is less than 5. Monochloramine is more stable and can be present in water for a longer period of time. After the mass ratio of the effective chlorine of the sodium hypochlorite to the ammonia nitrogen is greater than 5, monochloramine is further converted into dichloramine along with the gradual increase of the sodium hypochlorite input amount, and the dichloramine is partially converted into nitrogen escaping water under a proper condition. According to the fifth reaction formula, a large amount of hypochlorous acid is released while the dichloramine is decomposed into nitrogen, the hypochlorous acid reacts with monochloramine to generate more dichloramine, and the aim of thorough denitrification under the condition of no redundant effective chlorine is quickly achieved through the cyclic reaction.
Examples of the experiments
In the experimental example, the reagent ammonium chloride is dissolved in tap water to prepare simulated wastewater with the ammonia nitrogen content of 5mg/L, the actual volume of the reactor 1 is 50 liters, and the method comprises the following specific steps:
opening an ammonia nitrogen wastewater inlet pump 4 and a sodium hypochlorite feeding pump 6, fully mixing ammonia nitrogen wastewater to be treated and added sodium hypochlorite through a pipeline mixer 3, and then flowing into a reactor 1, wherein the weight ratio of the effective chlorine addition of the sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated is 7.6: 1;
(II) detecting the oxidation-reduction potential value of the mixed liquid entering the reactor 1 in real time by the ORP controller, and adjusting the flow of the sodium hypochlorite feeding pump 6 in real time according to the display value detected by the ORP controller so as to control the dosage of the sodium hypochlorite in real time; when the display value detected by the ORP controller reaches the range of 620-;
thirdly, when the mixed liquid entering the reactor 1 reaches the designated liquid level, closing the ammonia nitrogen wastewater inlet pump 4 and the sodium hypochlorite feeding pump 6, and stopping the mixed liquid entering the reactor 1; starting the hydrodynamic cavitation oxygen aeration machine 2 and the ozone generator 5, adjusting a flow meter of the ozone generator 5, adding the output ozone into the mixed liquid at a flow rate of 0.6-0.8 mg/min per liter of the mixed liquid, and fully reacting the ozone with ammonia nitrogen in a micron-sized bubble form under the hydrodynamic cavitation action to realize complete denitrification without residual chlorine; in the reaction process, the ORP controller detects the reaction degree of the mixed liquid in the reaction process in real time; detecting the high-efficiency mixing reaction time of the micron-sized bubbles and the mixed liquid to be 10min, 15min and 20min respectively, sampling and detecting indexes of residual chlorine and ammonia nitrogen in the sample when the preset time is reached, wherein the experimental data are shown in tables 1 and 2;
fourthly, when the oxidation-reduction potential value detected by the ORP controller 9 reaches the designated value of 930-970mv and is stabilized for five minutes and the display value of the ammonia nitrogen on-line analyzer 10 reaches the designated value of 1mg/L or below, the mixed liquid in the reactor 1 is treated completely, and the hydrodynamic cavitation, oxygenation and aeration machine 2 and the ozone generator 5 are closed; the experimental data are shown in Table 3;
(V) opening the drain valve 8 of the reactor 1 to discharge the treated mixed solution from the reactor.
As can be seen from tables 1 and 2, when the mass ratio of chlorine to nitrogen in the mixed liquor in the reactor 1 is 7.6-8.0, 0.6mg/min and 0.8mg/min of ozone is added to each liter of the mixed liquor, the mixed liquor is reacted for 20min, the residual chlorine in the mixed liquor is minimum, the ammonia nitrogen is minimum, and the purposes of denitrification and chlorine reduction are achieved, so the weight ratio of the effective chlorine adding amount of the selected sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated is 7.6-8: 1. The adding amount of the ozone is 0.6-0.8 mg/min/liter of the mixed solution. As can be seen from Table 3, when the reaction time is 15 to 20min, the display value of the ORP controller is 945 to 973, that is, the reaction degree is controlled by the display value of the ORP controller.
TABLE 1 residual chlorine Change (mg/L)
TABLE 2 degradation of Ammonia nitrogen (mg/L)
TABLE 3ORP Change (mv)
In order to compare the treatment effects of the method of the invention and the conventional breakpoint chlorination method, a comparison test of conventional breakpoint chlorination method denitrification and the method of the invention is carried out under the same conditions. The experimental result is shown in figure 2, the simulated wastewater with the ammonia nitrogen content of 5mg/L is treated, the ammonia nitrogen content is the lowest when the mass ratio of chlorine to nitrogen is 8.0 by the conventional breakpoint chlorination method, and the residual chlorine value in the water reaches the lowest value of 1.5 mg/L. FIG. 2 is a comparison of the ammonia nitrogen content in water treated by the method of denitrification with conventional breakpoint chlorination and the ammonia nitrogen content in water treated by the method of the present invention with the reaction time when the mass ratio of chlorine to nitrogen is 7.6.
Claims (3)
1. The method for deeply treating nitrogen and chlorine in wastewater by using one-step method of ozone and chlorine oxidation is characterized by comprising the following steps of:
1) adding ammonia nitrogen wastewater to be treated and sodium hypochlorite into a pipeline mixer at the same time, fully mixing to form a mixed solution, and flowing into a reactor; the weight ratio of the effective chlorine addition amount of the sodium hypochlorite to the ammonia nitrogen in the ammonia nitrogen wastewater to be treated is 7.6-8: 1;
2) the ORP controller detects the oxidation-reduction potential value of the mixed liquid entering the reactor in real time, and adjusts the flow of the sodium hypochlorite feeding pump in real time according to the display value detected by the ORP controller so as to control the dosage of the sodium hypochlorite; when the display value detected by the ORP controller reaches the range of 620-;
3) when the mixed liquid entering the reactor reaches the designated liquid level, closing the ammonia nitrogen wastewater inlet pump and the sodium hypochlorite feeding pump, and stopping the mixed liquid entering the reactor; starting the hydrodynamic cavitation oxygen aeration machine and the ozone generator, adjusting a flow meter of the ozone generator, adding the output ozone into the mixed liquid at a flow rate of 0.6-0.8 mg/min per liter of the mixed liquid, and fully reacting the ozone with ammonia nitrogen in a micron-sized bubble form under the hydrodynamic cavitation action to realize complete denitrification without residual chlorine; in the reaction process, the ORP controller detects the reaction degree of the mixed liquid in the reaction process in real time;
4) when the oxidation-reduction potential value detected by the ORP controller reaches the designated value of 930-970mv and is stabilized for five minutes and the display value of the ammonia nitrogen online analyzer reaches the designated value of 1mg/L or below, the mixed liquid in the reactor is treated completely, and the hydrodynamic cavitation oxygen aeration machine and the ozone generator are closed;
5) the drain valve of the reactor was opened to drain the treated mixed solution from the reactor.
2. The one-step method of ozone-assisted oxychlorination advanced treatment of nitrogen and chlorine in wastewater according to claim 1, wherein the method comprises the following steps: the sodium hypochlorite can be replaced by any one of chlorine, chlorine dioxide, calcium hypochlorite or dichloroisocyanuric acid.
3. The device for the advanced treatment of nitrogen and chlorine in wastewater by the one-step method of ozone in cooperation with oxychlorination as claimed in claim 1 or 2, which is characterized in that: the device consists of a reactor (1), a hydrodynamic cavitation aeration machine (2), a pipeline mixer (3), an ammonia nitrogen wastewater inlet pump (4), an ozone generator (5), a sodium hypochlorite feeding pump (6), a sodium hypochlorite dissolver (7), a drain valve (8), an ORP controller (9) and an ammonia nitrogen online analyzer (10), wherein the hydrodynamic cavitation aeration machine (2) is arranged in the reactor (1), an air inlet of the hydrodynamic cavitation aeration machine (2) is connected with an air outlet of the ozone generator (5), a water inlet of the ammonia nitrogen wastewater inlet pump (4) is connected with a wastewater pool, a water outlet of the ammonia nitrogen wastewater inlet pump (4) is connected with a wastewater inlet of the pipeline mixer (3), a water outlet of the pipeline mixer (3) is connected with a water inlet of the reactor (1), a feed inlet of the sodium hypochlorite feeding pump (6) is connected with the sodium hypochlorite dissolver (7), the discharge hole of the sodium hypochlorite feeding pump (6) is connected with the feed inlet of the pipeline mixer (3), the test heads of the ORP controller (9) and the ammonia nitrogen online analyzer (10) are arranged in the reactor (1), the ORP controller (9) and the ammonia nitrogen online analyzer (10) respectively detect and control the addition amount and the reaction time of the sodium hypochlorite, and the drain valve (8) is arranged at the bottom of one side of the reactor (1).
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