CN103508546A - Method for implementing rapid start of short-cut nitrification and denitrification to treat wastewater by preposed pre-oxidation - Google Patents
Method for implementing rapid start of short-cut nitrification and denitrification to treat wastewater by preposed pre-oxidation Download PDFInfo
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Abstract
The invention relates to a method for implementing rapid start of short-cut nitrification and denitrification to treat wastewater by preposed pre-oxidation. In the method, before short-cut nitrification and denitrification processing is carried out on high ammonia-nitrogen wastewater, organic acid is added into the wastewater to carry out pre-oxidation on the wastewater. According to the method, by adding the organic acid, hydrogen ions are provided for a reaction system; the organic acid is combined with nitrate contained in the high ammonia-nitrogen wastewater to form an acidic oxidation environment; conversion from nonbiodegradable macromolecular substances to small molecular substances capable of being utilized by microorganisms is promoted; organisms which are toxic and harmful to ammonia-oxidizing bacteria are subjected to ring opening or chain breaking and are decomposed into small molecules; on one hand, the pre-oxidation process can reduce toxicity of the wastewater on the microorganisms, improve biodegradability of the wastewater and provide an excellent external environment for short-cut nitrification and denitrification of floras, and on the other hand, the pre-oxidation process also can provide a carbon source for the subsequent nitrification process.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, relate in particular to a kind of method that realizes the reaction of quick startup short-cut nitrification and denitrification in the treating processes of waste water by preposition acid adding preoxidation.
Background technology
Refining catalytic agent production waste water is mainly the waste water that catalyst for heavy oil catalytic cracking is produced, and its production process is used a large amount of ammonium salts and ammoniacal liquor, and high ammonia-nitrogen wastewater is the inevitable outcome of oil refining catalyst production process.Catalyzer sewage quality is complicated, has that suspended substance and ammonia nitrogen concentration are high, fluctuating range large (60mg/L～300mg/L), complicated component and a feature such as B/C value is low, and more difficult realization is carried out a biological disposal upon.Conventional treatment process comprises materialization treatment process (as blow-off method and break point chlorination method etc.) and biological treatment at present.Traditional biological treatment is current most widely used denitride technology, and using the physiological metabolism effect of microorganism is nitrate by mineralized nitrogen, then realizes thorough denitrogenation by denitrification.
Mainly there is following problem in traditional biologic treating technique: technical process is long, floor space is large and initial cost expense is high; During winter low temperature, microorganism active is low, easily causes treatment effect unstable; The HRT of system is longer, needs compare great aeration tank, has increased investment and working cost; System is to maintain higher biological concentration and obtain good denitrification effect, must carry out mud and nitrification liquid simultaneously and reflux, and has increased power consumption and working cost; System impact resistance a little less than, high-concentration ammonia nitrogenous wastewater can suppress nitrobacteria growth, processing costs is higher, but also likely causes secondary pollution.
Summary of the invention
For overcoming the above-mentioned defect under prior art, the object of the present invention is to provide a kind of preposition preoxidation to realize and start fast the method that short-cut nitrification and denitrification is processed waste water, can start fast at short notice short-cut nitrification and denitrification process, realize the economical and efficient of oil refining catalyst waste water and process.
The technical solution used in the present invention is: a kind of preposition preoxidation realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, before high ammonia-nitrogen wastewater is carried out to short-cut nitrification and denitrification processing, to adding organic acid in waste water, waste water is carried out to preoxidation.
Described organic acid is preferably acetic acid.
The addition of described acetic acid can be for adding 2.5～3.5g acetic acid containing in the waste water of every gram of ammonia nitrogen.
Conventionally, continue waste water to stir in the preoxidation process of waste water, the time of pre-oxidation treatment is 30～60min.
Present method can be added sanitary sewage adding acetic acid in waste water when, and described sanitary sewage can be municipal wastewater and/or Residential areas sewage, and the acetic acid of interpolation and the molar concentration rate of the nitrate radical in sanitary sewage are preferably greater than 1 and be less than 2.
Preferably, regulate the aeration rate of waste water in short distance nitration reaction process, making the dissolved oxygen concentration in waste water is 0.5～1.0mg/L.
In the treating processes of waste water, can in the waste water carrying out in short distance nitration reaction process, add mud, described mud can be the mud of municipal sludge and/or waste water treatment plant's generation.
Further, can in the waste water carrying out in short distance nitration reaction process, add alkali, regulating the pH value of waste water is 8.0～8.5.
Generally, waste water is processed in reactor, described reactor can comprise vertical cylindrical shell, in described housing, can coaxially be provided with vertical hollow, the bottom of described hollow can be fixedly connected with the bottom of described housing, the top of described hollow is opened wide, the part that the top of described housing is at least closed on described hollow open wide and the top of described hollow higher than the top of described housing, or the top of described hollow is opened wide and is communicated with the internal space of described housing, in described hollow, can be provided with stirring rake, preferably, annular space between described hollow and described housing is divided into the upper and lower two portions in aerobic zone and oxygen-starved area, the bottom of described aerobic zone can be provided with microporous aeration device, in described oxygen-starved area, can be filled with the filler for promoting that anti-nitration reaction carries out.
The bottom of described hollow can be provided with and is communicated with it and extends to the water inlet pipe outside described housing, and the bottom of described housing can be provided with and is communicated with described annular space and extends to the rising pipe outside described housing.
Beneficial effect of the present invention: the present invention is by carrying out preoxidation to carrying out adding organic acid in short-cut nitrification and denitrification waste water before, for reaction system provides hydrogen ion, in conjunction with the nitrate radical containing in high ammonia-nitrogen wastewater (with the sanitary sewage adding with organic acid simultaneously), form acidic oxidation environment (can carry out after stable reaction sewage backflow so that nitrate radical to be provided) to a certain degree, promoted that difficult for biological degradation macromolecular substance (will be poisonous to ammonia oxidation bacteria to the conversion of the small-molecule substance that can utilize for microorganism, harmful organism open loop or chain rupture, be decomposed into small molecules).Preoxidation process can reduce the toxicity of waste water to microorganism on the one hand, improve the biodegradability of waste water self, for short distance nitration and denitrification flora provide good outside atmosphere, also can provide carbon source for follow-up nitration reaction process on the other hand, according to applicant's experiment, according to this method for pre-oxidizing, can effectively improve the biodegradability (BOD of refining catalytic agent production waste water
5/ COD
crcan improve 32-50%).
In preoxidation process, continue waste water to stir, both be conducive to hydrogen ion in the organic acid nitrate ion in waste water and be combined and form acidic oxidation environment, and can further promote again the macromolecular substance of difficult for biological degradation to transform to the small-molecule substance that can utilize for microorganism.
To adding organic acid in waste water, add sanitary sewage simultaneously, improved the content of nitrate radical in waste water, be conducive to accelerate the reaction tendency that nitrate radical is combined with hydrogen ion, promote the formation of acidic oxidation environment.
Regulate the aeration rate of waste water in short distance nitration reaction process, be conducive to the accumulation of ammonia oxidation bacteria, meanwhile, lower dissolved oxygen also provides anoxic-anaerobic environment for the microbial film of the filling surface in anti-nitration reaction process, is beneficial to carrying out smoothly of denitrification process.
In the waste water carrying out in short distance nitration reaction process, add appropriate active sludge, can improve the content of microorganisms in waste water, avoid due to the too low process that affects subsequent reactions of the content of microorganisms in waste water under low aeration rate.
Reactor is divided into preoxidation district, aerobic zone and oxygen-starved area, and preoxidation process, short distance nitration and denitrification process have been carried out to effective separation, is convenient to each reaction process to carry out respectively regulation and control.The rationalization partition of acid adding preoxidation and reactor, strengthens the treatment rate of denitrogenation of waste water, and can be microorganism good outside growing environment is provided, thereby accelerates the startup speed of short-cut nitrification and denitrification process.The method also has the aeration rate of saving, reduces energy consumption, saves denitrifying carbon source, saves reactor volume and reduces the features such as sludge yield, can also be by adjusting organic acid and sanitary sewage dosage, sewage backflow amount and the residence time of waste water in each reaction process, realize good Nitrogen removal effect, effectively resist mud impact load.
Accompanying drawing explanation
Fig. 1 is the structural representation of reactor of the present invention;
Fig. 2 is the short distance nitration design sketch of experimental example of the present invention.
Embodiment
The invention provides a kind of preposition preoxidation and realize and start fast the method that short-cut nitrification and denitrification is processed waste water, before high ammonia-nitrogen wastewater is carried out to short-cut nitrification and denitrification processing, to adding organic acid in waste water, waste water is carried out to preoxidation.By organic acid, add, for reaction system provides hydrogen ion, in conjunction with the nitrate radical containing in high ammonia-nitrogen wastewater (with the sanitary sewage adding with organic acid simultaneously), form acidic oxidation environment (can carry out after stable reaction sewage backflow so that nitrate radical to be provided) to a certain degree, promoted the conversion (organism open loop or chain rupture by ammonia oxidation bacteria poisonous, harmful, be decomposed into small molecules) of difficult for biological degradation macromolecular substance to the small-molecule substance that can utilize for microorganism.Preoxidation process on the one hand can reduce the toxicity of waste water to microorganism, improves the biodegradability of waste water self, for short distance nitration and denitrification flora provide good outside atmosphere, also can provide carbon source for follow-up nitration reaction process on the other hand.
After stable reaction, can be by urceolus effluent recycling to inner core, so that nitrate root to be provided, the described backflow water yield is not more than conventionally into 1/5 of water total amount, and the water yield that conventionally refluxes is about 1/6 of reactor total inflow.
Conventionally, in the preoxidation process of waste water, continue waste water to stir, both be conducive to hydrogen ion in the organic acid nitrate ion in waste water and be combined and form acidic oxidation environment, and can further promote again the macromolecular substance of difficult for biological degradation to transform to the small-molecule substance that can utilize for microorganism.Preferably, the time of pre-oxidation treatment is 30～60min.
Described organic acid is preferably acetic acid, and its addition can be for adding 2.5～3.5g acetic acid containing in the waste water of every gram of ammonia nitrogen.
Present method can be added sanitary sewage adding acetic acid in waste water when, and described sanitary sewage can be municipal wastewater and/or Residential areas sewage, and the acetic acid of interpolation and the molar concentration rate of the nitrate radical in sanitary sewage are preferably greater than 1 and be less than 2.The interpolation of described sanitary sewage has improved the content of nitrate radical in waste water, is conducive to accelerate the reaction tendency that nitrate radical is combined with hydrogen ion, promotes the formation of acidic oxidation environment.
Preferably, regulate the aeration rate of waste water in short distance nitration reaction process, making the dissolved oxygen concentration in waste water is that 0.5～1.0mg/L(is as 0.5 mg/L, 0.6 mg/L, 0.8 mg/L or 1.0 mg/L), be conducive to the accumulation of ammonia oxidation bacteria, simultaneously, lower dissolved oxygen also provides anoxic-anaerobic environment for the microbial film on the condiment surface in denitrification process, is beneficial to carrying out smoothly of denitrification process.
In the treating processes of waste water, according to the processing total amount of waste water, can in the waste water carrying out in short distance nitration reaction process, add appropriate mud, to improve the content of microorganisms in waste water, avoid due to the too low process that affects subsequent reactions of the content of microorganisms in waste water under low aeration rate.Described mud can be the mud of municipal sludge and/or waste water treatment plant's generation.
Further, can in the waste water carrying out in short distance nitration reaction process, add alkali, regulating the pH value of waste water is 8.0～8.5, and to promote the carrying out of short distance nitration process, the alkali of interpolation can be sodium carbonate.
Generally, waste water is processed in reactor, referring to Fig. 1, described reactor can comprise vertical cylindrical shell 1, in described housing, can coaxially be provided with vertical hollow 2, the internal space of described hollow is the preoxidation district 3 of waste water, the bottom sealing of described hollow is also fixedly connected with the bottom of described housing, the bottom of described hollow can extend to outside the bottom of described housing, also can be positioned at the inside of housing, when the bottom of described hollow extends to outside the bottom of described housing, the two sealing, when the bottom of described hollow is positioned at described housing, the two can seal also can leave gap, the top of described hollow and described housing can adopt following two kinds of modes to arrange: the top that a kind of mode is described hollow is opened wide, the part that the top of described housing is at least closed on described hollow open wide and the top of described hollow higher than the top of described housing, so that the waste water in described preoxidation district can flow into the space between described hollow and described housing, and waste water in space between described hollow and described housing can not flow backward to described preoxidation district, preferably, the top of described housing is all opened wide, the top that another kind of mode is described hollow is lower than the top of described housing, the top of described hollow is opened wide and is communicated with the internal space of described housing, due to the top lower than described housing, the top of described hollow, when adopting this kind of mode, should note controlling the liquid level of the waste water in the space between described hollow and described housing, make it remain the top lower than described hollow, to prevent that the waste water in the space between described hollow and described housing from flowing backward to described preoxidation district.In described hollow, can be provided with stirring rake 4, conveniently the waste water in preoxidation district is stirred, preferably, annular space between described hollow and described housing is divided into aerobic zone 5 and oxygen-starved area two portions Shang Xia 6, the bottom of described aerobic zone can be provided with microporous aeration device 7, short distance nitration process aeration at waste water, can be filled with the filler (biofilm carrier) 8 for promoting anti-nitration reaction to carry out in described oxygen-starved area.The bottom of described hollow can be provided with and is communicated with it and extends to the water inlet pipe 9 outside described housing, for inject waste water, organic acid and sanitary sewage in described preoxidation district, the bottom of described housing can be provided with and is communicated with described annular space (or oxygen-starved area) and extends to the rising pipe 10 outside described housing, waste water after described reactor for treatment can be discharged described reactor by described rising pipe, on described water inlet pipe and rising pipe, all can be provided with valve.Described reactor can also be provided with mud inlet pipe, its entrance connects mud source, outlet is communicated with described aerobic zone or when the top of described housing is opened wide, is positioned at the top of described aerobic zone or stretches into described aerobic zone, for the short distance nitration process at waste water, in waste water, adds mud.
Described reactor is divided into preoxidation district, aerobic zone and oxygen-starved area, and the preoxidation process of waste water, short distance nitration and denitrification process have been carried out to effective separation, is convenient to each reaction process to carry out respectively regulation and control.The rationalization partition of acid adding preoxidation and reactor, can effectively improve the biodegradability (BOD/COD can improve 32-50%) of catalyst production waste water, strengthen the treatment rate of denitrogenation of waste water, and can be microorganism good outside growing environment is provided, thereby accelerate the startup speed of short-cut nitrification and denitrification process.The method also has the feature of saving aeration rate, reducing energy consumption, saving denitrifying carbon source (reaching 40% left and right), save reactor volume and reduction sludge yield, the residence time that can also gather in each reaction process by adjusting organic acid and sanitary sewage dosage, sewage backflow amount and waste water, realize good Nitrogen removal effect, effectively resist mud impact load.
Experimental example:
Oil refining sewerage treatment plant of seed sludge Wei Mou petro-chemical corporation catalyst production waste water processing unit returned sluge, inoculum size is 0.8L, sludge concentration 3257mg/L in inoculation post-reactor moves reactor under 33 ℃, the condition of dissolved oxygen 0.5mg/L.Containing wastewater from catalyst is high ammonia nitrogen, low-carbon (LC) waste water, and contain a large amount of salts and difficult bioavailable larger molecular organics and reducing substances, water-quality constituents is complicated, intractability is larger, its main water-quality guideline is as shown in table 1, reactor operating performance as shown in Figure 2, the municipal wastewater that sanitary sewage is on-site.
In the treating processes of waste water, waste water enters the preoxidation district of reactor by the water inlet pipe of reactor, to adding acetic acid and sanitary sewage in waste water, it is carried out to appropriateness oxidation, acetic acid and sanitary sewage can add by water inlet pipe, also can add by other pipeline being communicated with water inlet pipe or preoxidation district, the wastewater biodegradability raising of process preoxidation reaches 40%(BOD
5/ COD
crcan bring up to 0.35 from 0.25), in waste water, ammonia-nitrogen content is higher.Afterwards, the water outlet in described preoxidation district enters the aerobic zone of reactor and carries out short distance nitration, after nitration treatment, ammonia nitrogen is transformed into nitrite nitrogen, and under the effect of the oxygen-starved area of reactor heterotrophic bacterium, further denitrification generates nitrogen, realizes the short-cut nitrification and denitrification process of high ammonia-nitrogen wastewater.In denitrification process, heterotrophic bacterium utilizes is the carbon source that after preoxidation, acetic acid and waste water self provide.
Referring to Fig. 2, in 1st～60 cycles, adopt the disposable mode that adds acetic acid and sanitary sewage to move reactor, with this understanding, there is the accumulation of nitrite, nitrous accumulation rate maintains between 60%～80% always.Since the 60th cycle, according to the data of 1～60 cycle gained, the amount of calculating gained acetic acid and sanitary sewage is added in batches, when mixed solution enters behind aerobic zone, suitably adjusting pH value is 8.0～8.5.In follow-up 5 cycles, move in this way continuously reactor, as can be seen from Figure 2, reactor at short notice nitrite accumulation rate rises to 90% by 60%, and can stablize and remain on more than 90%, through follow-up denitrification process, can realize more up hill and dale denitrogenation again.
Catalyst production waste water contains a large amount of toxic substances and hardly degraded organic substance, if not to its carry out preoxidation short distance nitration process be difficult to start, himself contained organism that utilizes also cannot meet the demand of denitrification process to carbon source, therefore in the treating processes of waste water, needs former water to carry out suitable pre-treatment regulation and control operating parameter in time.The water quality characteristics of combined catalyst waste water of the present invention, prepositionly adds organic acid and sanitary sewage carries out preoxidation, forms acidic oxidation environment, increases follow-up microorganism and can utilize carbon source, improves the biodegradability of waste water.Suitable aeration rate in rationalization partition by reactor and short distance nitration process subsequently, successfully realized the accumulation of cigarette nitrate, last waste water enters oxygen-starved area, and a large amount of denitrifying bacteriums that are attached on oxygen-starved area biofilm carrier (filler) start to utilize sufficient carbon source to carry out denitrification to complete final denitrogenation.
Claims (10)
1. preposition preoxidation realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that before high ammonia-nitrogen wastewater is carried out to short-cut nitrification and denitrification processing, to adding organic acid in waste water, waste water is carried out to preoxidation.
2. preposition preoxidation according to claim 1 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that described organic acid is acetic acid.
3. preposition preoxidation according to claim 2 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that the addition of described acetic acid is for adding 2.5～3.5g acetic acid containing in the waste water of every gram of ammonia nitrogen.
4. preposition preoxidation according to claim 3 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that in the preoxidation process of waste water continuing waste water to stir, and the time of pre-oxidation treatment is 30～60min.
5. preposition preoxidation according to claim 4 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, when it is characterized in that adding acetic acid in waste water, add sanitary sewage, described sanitary sewage is municipal wastewater and/or Residential areas sewage, and the acetic acid of interpolation and the molar concentration rate of the nitrate radical in sanitary sewage are greater than 1 and be less than 2.
6. preposition preoxidation according to claim 5 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that regulating the aeration rate of waste water in short distance nitration reaction process, and making the dissolved oxygen concentration in waste water is 0.5～1.0mg/L.
7. preposition preoxidation according to claim 6 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that adding active sludge in the waste water carrying out in short distance nitration reaction process, described mud is the active sludge that municipal sludge and/or waste water treatment plant produce.
8. preposition preoxidation according to claim 7 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that adding alkali in the waste water carrying out in short distance nitration reaction process, and regulating the pH value of waste water is 8.0～8.5.
9. according to claim 1, 2, 3, 4, 5, 6, preposition preoxidation described in 7 or 8 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, it is characterized in that waste water processes in reactor, described reactor comprises vertical cylindrical shell, in described housing, be coaxially provided with vertical hollow, the bottom of described hollow is fixedly connected with the bottom of described housing, the top of described hollow is opened wide, the part that the top of described housing is at least closed on described hollow open wide and the top of described hollow higher than the top of described housing, or the top of described hollow is opened wide and is communicated with the internal space of described housing, in described hollow, be provided with stirring rake, annular space between described hollow and described housing is divided into the upper and lower two portions in aerobic zone and oxygen-starved area, the bottom of described aerobic zone is provided with microporous aeration device, in described oxygen-starved area, be filled with the filler for promoting that anti-nitration reaction carries out.
10. preposition preoxidation according to claim 9 realizes and starts fast the method that short-cut nitrification and denitrification is processed waste water, the bottom that it is characterized in that described hollow is provided with and is communicated with it and extends to the water inlet pipe outside described housing, and the bottom of described housing is provided with and is communicated with described annular space and extends to the rising pipe outside described housing.
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| CN105923752A (en) * | 2016-05-23 | 2016-09-07 | 沈阳师范大学 | Method for achieving shortcut nitrification by utilizing formic acid |
| CN114853274A (en) * | 2022-04-28 | 2022-08-05 | 南京神克隆科技有限公司 | High-efficiency integrated treatment process for landfill leachate membrane concentrated solution |
| CN116514287A (en) * | 2023-07-03 | 2023-08-01 | 成都理工大学 | Nitrate wastewater domestic sewage synchronous treatment device, system and method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105923752A (en) * | 2016-05-23 | 2016-09-07 | 沈阳师范大学 | Method for achieving shortcut nitrification by utilizing formic acid |
| CN105923752B (en) * | 2016-05-23 | 2019-01-25 | 沈阳师范大学 | The method for realizing short distance nitration using formic acid |
| CN114853274A (en) * | 2022-04-28 | 2022-08-05 | 南京神克隆科技有限公司 | High-efficiency integrated treatment process for landfill leachate membrane concentrated solution |
| CN116514287A (en) * | 2023-07-03 | 2023-08-01 | 成都理工大学 | Nitrate wastewater domestic sewage synchronous treatment device, system and method |
| CN116514287B (en) * | 2023-07-03 | 2023-09-08 | 成都理工大学 | Nitrate wastewater domestic sewage synchronous treatment device, system and method |
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