CN103601286A - A method for achieving nitrite accumulation during nitrate reduction - Google Patents
A method for achieving nitrite accumulation during nitrate reduction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000009825 accumulation Methods 0.000 title claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 5
- 230000009467 reduction Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010802 sludge Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011946 reduction process Methods 0.000 claims abstract description 11
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- 239000001632 sodium acetate Substances 0.000 claims description 12
- 235000017281 sodium acetate Nutrition 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 239000002417 nutraceutical Substances 0.000 claims description 3
- 235000021436 nutraceutical agent Nutrition 0.000 claims description 3
- 238000012163 sequencing technique Methods 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 2
- 241000976983 Anoxia Species 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 230000007953 anoxia Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
A method for realizing nitrite accumulation in the nitrate reduction process belongs to the technical field of water treatment and is realized by the following steps that firstly, the type and concentration of sludge are selected, and the sludge concentration of a reactor is set to be 1000-1500 mg/L; selecting a carbon source and setting a carbon-nitrogen ratio, wherein C/N is up to 2.5: 1, the ratio of C/N is 2.5: 1, instantly injecting raw water into a reactor with preset sludge for stirring and mixing muddy water, feeding water again by virtue of pH indication, stopping reaction when the water amount in the reactor reaches the upper limit of the volume of the reactor after the last period is finished or when the pH value is more than 9.5 after the inflection point appears on the pH curve, precipitating for 10-15min, performing muddy water separation, and discharging water after the precipitation is finished. The method has the advantages of high denitrification rate, simple maintenance, low cost and no need of professional operation.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of method of sewage disposal.
Background technology
In China, northern area particularly, underground water is the important drinking water source of a class.Yet the below standard discharge of municipal effluent secondary treatment yielding water makes a large amount of NO that contains
3 --N waste water enters earth's surface or body of groundwater, the safety of potential threat drinking water source.Thereby no matter in city or rural area, the advanced nitrogen of sewage becomes a great society problem increasingly.Owing to being subject to the restriction of low-carbon and nitrogen (C/N) ratio, for the advanced nitrogen of municipal effluent, at present, comparatively extensive by adding the rear-mounted denitrification process application of outer carbon source.Yet this technique tends to increase running cost and sludge disposal difficulty in the denitrification effect of realizing ideal.In addition, the out of true of additional carbon also adds can affect effluent quality, forms secondary pollution.
In recent years, as a new bio autotrophic denitrification technique, half short distance nitration-anaerobic ammoxidation (Partial Nitritation-Anammox) is with NH
4 +-N, can be by the NO of short distance nitration generation as electron donor
2 --N reduction, final product is N
2with a small amount of NO
3 --N.It is expected to become low C/N than effective Approach of Removal of Nitrogen of municipal effluent because of higher efficiency and less energy-consumption.But formula 1 shows, under the sufficient condition that reacts completely, in anaerobic ammonia oxidation reactor, 10% nitrogen element is still with NO
3 -the form of-N is present in water outlet.
1 NH
4 + + 1.32 NO
2 - + 0.066 HCO
3 - + 0.13 H
+
→1.02 N
2 + 0.26 NO
3 - + 0.066 CH
2O
0.5N
0.15 + 2.03 H
2O (1)
In view of this, half single short distance nitration-anaerobic ammoxidation system is difficult to realize advanced nitrogen.Limitation based on traditional rear-mounted denitrification and half short distance nitration-anaerobic ammoxidation technique, in recent years, a kind of coupling half short distance nitration-anaerobic ammoxidation and part denitrification (NO
3 --N → NO
2 -n) novel denitrification system receives publicity increasingly.As shown in Figure 1, in this system, in theory, the NO in half short distance nitration-anaerobic ammoxidation reactor water outlet
3 --N is reduced to NO by internal reflux in part denitrification reactor
2 --N, enters after half short distance nitration-anaerobic ammoxidation reactor again, finally changes into N
2.
At present, scientific research and engineering circles are mostly devoted to the realization of half short distance nitration-anaerobic ammoxidation system with stable, and have obtained good result.But for part denitrification (NO
3 --N → NO
2 --N) system, by known to the Methanogenesis of traditional heterotrophic denitrification (formula 2), by optimization of operating parameters, by NO
3 --N reduzate is farthest controlled as NO
2 --N also realizes stable NO
2 --N accumulation volume is problem demanding prompt solution.
NO
3 - → NO
2 - → NO→ N
2O → N
2 (2) 。
Summary of the invention
The technical problem to be solved in the present invention is to disclose a kind of method that realizes nitrite accumulation in nitrate reduction process, thereby is part denitrification (NO
3 --N → NO
2 --N) the practical application supplying method of system, coupled half short distance nitration-anaerobic ammoxidation system.
The scheme of technical solution problem of the present invention comprises the following steps:
(i). select sludge types and concentration
Select the excess sludge of anoxic/aerobic activated sludge system that sludge age is greater than 30d as test mud.Before starting, reaction carries out the aerobic aeration of 2-3 hour, and place 2-3 hour, make under microorganism in the mud condition in existing without nutraceutical matrix, use afterwards washed with de-ionized water 3 times, be placed in sequencing batch activated sludge reactor (SBR), setting reactor sludge concentration is 1000-1500mg/L.
(ii). select carbon source and set carbon-nitrogen ratio
Select acetate as additional carbon, acetate is strong base-weak acid salt, and its aqueous solution presents weakly alkaline, and the concentration of acetate and pH have certain cognation.As shown in Figure 2, at NO
3 -in-N reduction process, follow the consumption of acetate, the flex point that on pH curve, appearance is first risen and declined afterwards, can accurately indicate exhausting of acetate.Utilize this pH flex point can accurately judge that in solution, whether COD concentration is sufficient.Wherein acetate can be sodium acetate or potassium acetate.
After selected carbon source, according to NO to be processed
3 --N concentration, controls acetate and adds containing NO
3 -after the former water of-N, COD concentration and NO that acetate is converted in solution
3 -the ratio of-N concentration---carbon-nitrogen ratio (C/N) reaches 2.5:1.
(iii). muddy water mixing is reacted
By the water feed apparatus of sbr reactor device, in the sbr reactor device of the preset mud of the instantaneous injection of former water that is 2.5:1 by C/N ratio.Sbr reactor device adopts the whipping apptss such as magnetic stirrer oar or impeller to carry out the mixing of muddy water.The result of accompanying drawing 3 shows, the condition that acetate exists is compared the condition that acetate exhausts and is more conducive to NO
3 -nO in-N reduction process
2 -the accumulation of-N.Therefore, in pH curve, occur falling after rising flex point time stop stirring.
(iv). by pH indication water inlet again
When pH curve occurs after flex point, in 3min, will contain acetate and NO
3 -the carbon-nitrogen ratio of-N is that 2.5 former water injects sbr reactor device by water feed apparatus again.(iii) similar with step, while there is flex point on pH curve, again to intake, the acetate concentration in assurance reactor is sufficient all the time, but prescribes a time limit when the interior water yield of water inlet post-reactor reaches on reactor volume, stops into water.
(v). when upper one-period finishes in post-reactor the water yield, reach the reactor volume upper limit or occur after flex point when pH curve, pH value is greater than at 9.5 o'clock, stopped reaction, precipitation 10-15min, carries out mud-water separation.
(vi). after completing precipitation, the water-freeing arrangement by sbr reactor device carries out draining.
When needs are proceeded to process, repeating step (iii) to step (vi).
The present invention compared with prior art, has the following advantages:
1. selected carbon source---acetate is compared with methyl alcohol, glucose, and denitrification rate is high, has advantage in efficiency; It is easy to obtain from the anaerobically fermenting of excess sludge simultaneously, is a kind of reproducible green carbon source, has economically advantage.
2. the accurate indication by pH, acetate being existed has realized under the operation of intermittent water inflow continuous mode, NO
3 -nO in-N reduction process
2 -the stable accumulation of-N.PH sensor has economy advantage in controlling in real time, and maintaining is simpler.
3. this part denitrification (NO
3 --N → NO
2 -n) system, after half short distance nitration-anaerobic ammoxidation coupling, the denitrification percent promoting is in theory 0.11-1/(8.92+8.92r-rNAR), and wherein r and NAR are respectively half short distance nitration-anaerobic ammoxidation system effluent recycling to reflux ratio and the part denilrification system NO of part denilrification system
3 -nO in-N reduction process
2 -the accumulation rate of-N.
4. control method of the present invention is simple, without expensive NO is installed
3 --N and NO
2 --N on-line sensor, expense is low; After pH value feedback system is set, can realize programming automation management, without professional, operate.
Accompanying drawing explanation
Fig. 1 is half short distance nitration-anaerobic ammoxidation coupling unit denitrification (NO
3 --N → NO
2 --N) system flowchart;
Fig. 2 is for take the NO that sodium acetate is carbon source
3 -pH and COD, NO in-N reduction process
3 --N, NO
2 -the relation of-N change in concentration;
Fig. 3 be carbon-nitrogen ratio be under 1.4-3.5 condition sodium acetate sufficient with spent condition under NO
2 -the comparison of-N accumulation rate;
Fig. 4 is part denitrification (NO under intermittent water inflow continuous operation mode
3 --N → NO
2 --N) operating performance of system.
Embodiment
Actual motion effect below in conjunction with accompanying drawing 4 describes the present invention in detail:
(i). select sludge types and concentration
Anoxic excess sludge in the anoxia/aerobic biological membrane reactor that selection sludge age is 40 ± 2d is as test mud.Before starting, reaction carries out the aerobic aeration of 2.5 hours, and place 2.5 hours, make under microorganism in the mud condition in existing without nutraceutical matrix, use afterwards washed with de-ionized water 3 times, be placed in the sequencing batch activated sludge reactor that useful volume is 3L (SBR), according to reactor volume, setting sludge concentration is 1200mg/L.
(ii). select carbon source and set carbon-nitrogen ratio
Select sodium acetate as additional carbon.At NO
3 -in-N reduction process, follow the consumption of sodium acetate, the similar flex point that on pH curve, appearance is first risen and declined afterwards, can accurately indicate exhausting of sodium acetate.Utilize this pH flex point can accurately judge that in solution, whether COD concentration is sufficient.
Sodium acetate is added to containing NO
3 -in-N sewage, according to NO to be processed
3 --N concentration, controlling the carbon-nitrogen ratio (C/N) forming after sodium acetate is 2.5.
(iii). muddy water mixing is reacted
Open the water feed apparatus of sbr reactor device, by peristaltic pump by C/N than being in the sbr reactor device of 2.5 the preset mud of the instantaneous injection of former water.Adopt magnetic stirring apparatus to carry out the mixing of muddy water.By the pH in pH sensor online reaction process, change, when flex point appears in pH curve, stop at once stirring.
(iv). by pH indication water inlet again
When pH curve occurs after flex point, in 3min, will contain sodium acetate and NO
3 -the carbon-nitrogen ratio of-N is that 2.5 former water injects sbr reactor device by water feed apparatus again.(iii) similar with step, while there is flex point on pH curve, again to intake, the sodium acetate concentration in assurance reactor is sufficient all the time, but prescribes a time limit when the interior water yield of water inlet post-reactor reaches on reactor volume, stops into water.
(v). when upper one-period finishes in post-reactor the water yield, reach the reactor volume upper limit or occur after flex point when pH curve, pH value is greater than at 9.5 o'clock, stopped reaction, precipitation 10-15min, carries out mud-water separation.
(vi). after completing precipitation, the water-freeing arrangement by sbr reactor device carries out draining.
The secondary effluent that the laboratory scale anoxia/aerobic biological membrane reactor of take discharges is background (COD=32mg/L, difficult for biological degradation; NO
2 --N=0.7 mg/L; NO
3 --N=15 mg/L, NH
4 +-N=0.6 mg/L), by adding NaNO
3make NO
3 --N concentration reaches 20.5mg/L, continues in water, to add appropriate sodium acetate, COD concentration and NO that it is converted into
3 -the ratio of-N is 2.7.According to the formed method operation of the present invention, in the situation that moving 3 cycles continuously, the stable NO that realizes
3 -nO in-N reduction process more than 60%
2 --N accumulation rate.
Claims (1)
1. in nitrate reduction process, realize a method for nitrite accumulation, its feature comprises the following steps:
(i). select sludge types and concentration
Select the excess sludge of anoxic/aerobic activated sludge system that sludge age is greater than 30d as test mud, before starting, reaction carries out the aerobic aeration of 2-3 hour, and place 2-3 hour, make under microorganism in the mud condition in existing without nutraceutical matrix, use afterwards washed with de-ionized water 3 times, be placed in sequencing batch activated sludge reactor, setting reactor sludge concentration is 1000-1500mg/L;
(ii). select carbon source and set carbon-nitrogen ratio
Select acetate as additional carbon, according to NO to be processed
3 --N concentration, controls acetate and adds containing NO
3 -after the former water of-N, COD concentration and NO that acetate is converted in solution
3 -the ratio of-N concentration---carbon-nitrogen ratio C/N reaches 2.5:1, and wherein acetate is sodium acetate or potassium acetate;
(iii). muddy water mixing is reacted
By the water feed apparatus of reactor, C/N, than in the reactor for the preset mud of the instantaneous injection of former water of 2.5:1, is carried out to muddy water to be uniformly mixed, during the flex point that occurs falling after rising in pH curve, stop stirring;
(iv). by pH indication water inlet again
When pH curve occurs after flex point, in 3min, will contain acetate and NO
3 -the carbon-nitrogen ratio of-N is that the former water of 2.5:1 passes through water feed apparatus injecting reactor again, while there is flex point on pH curve, water inlet again, guarantees that the acetate concentration in reactor is sufficient all the time, but in water inlet post-reactor, the water yield reaches on reactor volume and prescribes a time limit, and stops into water;
(v). when upper one-period finishes in post-reactor the water yield, reach the reactor volume upper limit or occur after flex point when pH curve, pH value is greater than at 9.5 o'clock, stopped reaction, precipitation 10-15min, carries out mud-water separation;
(vi). after completing precipitation, the water-freeing arrangement by reactor carries out draining.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291528A (en) * | 2014-10-12 | 2015-01-21 | 北京工业大学 | Device and method for advanced treatment of high-matrix wastewater by anaerobic ammonia oxidation/partial denitrification process |
| CN105330015A (en) * | 2015-10-09 | 2016-02-17 | 北京工业大学 | Largest nitrite accumulation method in denitrification process |
| CN105366804A (en) * | 2015-11-13 | 2016-03-02 | 天津大学 | Agent for promoting nitrite accumulation in biological denitrification process |
| CN107162324A (en) * | 2017-05-31 | 2017-09-15 | 浙江伊诺环保科技股份有限公司 | A kind of sodium acetate as sewage treatment plant's additional carbon application |
| CN113697947A (en) * | 2021-08-16 | 2021-11-26 | 北京工业大学 | Method and device for regulating and controlling denitrification degree and process of DEAMOX system based on pH |
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| CN101602545A (en) * | 2009-04-03 | 2009-12-16 | 北京工业大学 | A method for obtaining stable nitrite accumulation through denitrification of sewage |
| CN103241916A (en) * | 2013-05-12 | 2013-08-14 | 北京工业大学 | Method for realizing maximal accumulation of nitrite in sludge fermentation coupling denitrification process |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101602545A (en) * | 2009-04-03 | 2009-12-16 | 北京工业大学 | A method for obtaining stable nitrite accumulation through denitrification of sewage |
| CN103241916A (en) * | 2013-05-12 | 2013-08-14 | 北京工业大学 | Method for realizing maximal accumulation of nitrite in sludge fermentation coupling denitrification process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291528A (en) * | 2014-10-12 | 2015-01-21 | 北京工业大学 | Device and method for advanced treatment of high-matrix wastewater by anaerobic ammonia oxidation/partial denitrification process |
| CN104291528B (en) * | 2014-10-12 | 2016-03-02 | 北京工业大学 | Anammox/part denitrification process advanced treatment Super matrix waste water plant and method |
| CN105330015A (en) * | 2015-10-09 | 2016-02-17 | 北京工业大学 | Largest nitrite accumulation method in denitrification process |
| CN105366804A (en) * | 2015-11-13 | 2016-03-02 | 天津大学 | Agent for promoting nitrite accumulation in biological denitrification process |
| CN105366804B (en) * | 2015-11-13 | 2018-03-02 | 天津大学 | The medicament of nitrite accumulation during a kind of promotion biological denitrification |
| CN107162324A (en) * | 2017-05-31 | 2017-09-15 | 浙江伊诺环保科技股份有限公司 | A kind of sodium acetate as sewage treatment plant's additional carbon application |
| CN113697947A (en) * | 2021-08-16 | 2021-11-26 | 北京工业大学 | Method and device for regulating and controlling denitrification degree and process of DEAMOX system based on pH |
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Application publication date: 20140226 |