CN102040308A - Method for treating wastewater by combining catalytic oxidation with biological aerated filter - Google Patents
Method for treating wastewater by combining catalytic oxidation with biological aerated filter Download PDFInfo
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- CN102040308A CN102040308A CN2009101807731A CN200910180773A CN102040308A CN 102040308 A CN102040308 A CN 102040308A CN 2009101807731 A CN2009101807731 A CN 2009101807731A CN 200910180773 A CN200910180773 A CN 200910180773A CN 102040308 A CN102040308 A CN 102040308A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 238000005189 flocculation Methods 0.000 claims abstract description 18
- 230000016615 flocculation Effects 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 230000003311 flocculating effect Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000012545 processing Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
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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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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for treating wastewater by combining catalytic oxidation with a biological aerated filter, which sequentially comprises the following steps of: 1) adding all or part of the wastewater to be treated into a flocculating tank, performing flocculation sedimentation, and adding into an oxidation tank; 2) adding acid into the oxidation tank to regulate the pH value of the wastewater to be 0 to 6, adding an oxidant and a catalyst and performing catalytic oxidation reaction; and 3) adding the oxidized wastewater into a settling tank for settling, discharging supernatant, adding alkali to regulate the pH value to be 6 to 9, adding into the biological aerated filter for treating, and discharging; and making settled acidic sediments flow back to a dissolving tank, adding the acid to regulate the pH value until the sediments are completely dissolved, adding solution into the flocculating tank and performing flocculation sedimentation reaction on the solution and all or part of the wastewater to be treated. Compared with the prior art, the method reduces the consumption of the acid and the alkali and treatment cost.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment.
Background technology
Along with China's industrialization and process of urbanization, a large amount of industry and domestic pollutant are discharged in the environment, bring more and more serious pollution to water body.The water quality that worsens not only causes numerous regional water quality lacks of water, increases the cost that entire society obtains water resources, and even more serious is to go back the health of entail dangers to people, thereby need handle the waste water that contains pollutent, makes it can qualified discharge.Along with the continuous development of water technology, most waste water can both obtain handling, but for a long time, the processing of the organic waste water of biodegradability difference is the difficult point in the water technology always in the environment, also is the important difficult problem of puzzlement countries in the world environment circle.
Such waste water is because biodegradability is poor, be difficult to directly adopt biochemical method to handle, substantially there is not effect by the processing of ordinary methods such as common filtration and flocculation, and charcoal absorption even depth treatment technology cost is too high, membrane separation technique is because also there is certain difficulty in practical problemss such as investment costliness and film pollution on using.
The research of the biodegradability of catalyzed oxidation technical finesse in recent years difference organic waste water has obtained significant progress.The mechanism of catalyzed oxidation is to combine with oxygenant with catalyzer, produces active extremely strong free radical (as OH) in reaction; By the adduction between free radical and the organic compound, replacement, transfer transport, scission of link etc., make the macromole hardly degraded organic substance oxidative degradation in the water body become to be easy to biodegradable small-molecule substance, even directly be degraded into CO again
2And H
2O is near permineralization.Because it is simple to operate that the catalyzed oxidation technology has, react characteristics such as quick, become the focus that people study.But directly adopt catalyzed oxidation technical finesse waste water cost higher, and adopt the biodegradability of the method raising waste water of catalyzed oxidation, can effectively reduce the processing cost of waste water at method processing waste water, thereby obtain extensive studies by biochemistry.For example:
A.CN1724420A proposes a kind of method of chemical oxidizing-biological biological filtering tank associating water treatment, and this method adopts Fenton reagent-biological aerated filter process to handle chemical plant secondary biochemical water outlet, and the COD of processed waste water can reduce to 30mg/L.
B.CN16366893A proposes a kind of using up and helps Fenton's reaction, flocculation and microbiological deterioration coupling to handle the method for waste water, and its COD clearance can reach 98.9%.
But aforesaid method remains in problems such as the acid and alkali consumption amount are big, and industrial applications is restricted.
Summary of the invention
The objective of the invention is to propose the method that a kind of catalyzed oxidation associating BAF is handled waste water, with the processing cost of further reduction waste water.
The method of the processing waste water among the present invention is on the basis of conventional catalyst method for oxidation, and the mode that adds alkali and precipitation backflow after the employing reduces the consumption of soda acid, improves the treatment effect of catalyzed oxidation.
The method of processing waste water provided by the invention may further comprise the steps in order:
4) make pending waste water all or part of, enter oxidation pond through after flocculation basin carries out flocculation sediment;
5) add acid in oxidation pond, the pH value 0～8 of regulating waste water adds oxygenant and catalyzer and carries out catalytic oxidation;
6) waste water after the oxidation enters the settling bowl sedimentation, adds alkali after supernatant liquor is discharged and regulates pH value 5～9, enters BAF and handles the back discharge; The acidic precipitation that settles down is back to and adds acid in the dissolving tank and be adjusted to all dissolvings of precipitation, and solution enters flocculation basin and all or part of pending waste water carries out flocculation precipitation reaction.
The oxygenant that adopts among the present invention can be a kind of in hydrogen peroxide, ozone, hypochlorite, perchlorate, the persulphate, preferred hydrogen peroxide.
Catalyzer among the present invention can be to go back the ortho states transition metal ion, can be selected among Fe2+, Mn2+, Ni2+, Co2+, Cd2+, Cu2+, Ag+, Cr3+ and the Zn2+ one or more, preferred Fe2+, can derive from ferrous sulfate, iron protochloride, the Iron nitrate one or more, preferably sulfuric acid is ferrous.
The acid that the present invention adds can be a kind of in sulfuric acid, hydrochloric acid, the nitric acid, preferably sulfuric acid.
The alkali that adds among the present invention can be a kind of in sodium hydroxide, potassium hydroxide, sodium bicarbonate, the yellow soda ash, preferred sodium hydroxide.
According to the water quality situation of waste water, can also add coagulant aids to strengthen flocculating effect in flocculation basin in the present invention, the coagulant aids that is adopted can be one or more in polymerize aluminum chloride, bodied ferric sulfate, the polyacrylamide.
The ratio of the mass concentration of the COD in the oxygenant among the present invention and the waste water be 5: 1～1: 100 preferred 2: 1～1: 20.The mol ratio of oxygenant and catalyzer is 10: 1～1: 3, preferred 5: 1～1: 2.
The pH value of waste water can be 0～8 in the oxidation pond, preferred 2～6.Settling bowl supernatant liquor pH value 6～9, preferred 6-8.The pH value can be less than 2 in the dissolving tank, preferred 0.1～1.
The residence time of waste water in oxidation pond can be 10-120 minute, preferred 30-60 minute, the residence time in settling tank can be 5～500 minutes, preferred 10～300 minutes, the residence time in BAF can be 0.5～20 hour, preferred 1～10 hour.
Compared with prior art, the present invention has following advantage:
1, reduces the acid and alkali consumption amount, reduced processing cost.
2, before catalytic oxidation, carry out flocculation sediment in advance and handle, improved the treatment effect of waste water.
3, the minimizing of acid and alkali consumption amount can also reduce the salts contg in the waste water, is beneficial to the processing of follow-up reusing sewage.
4, adopt the processing mode of catalyzed oxidation associating BAF, both made the waste water of difficult for biological degradation obtain handling, reduced the cost of independent employing catalyzed oxidation art breading again.
Description of drawings
Fig. 1 is the schematic flow sheet of catalyzed oxidation associating BAF treatment process of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Handle not standard discharge waste water of certain refinery, adopt H
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, used soda acid is dense H
2SO
4And NaOH.Operational condition is: H
2O
2With the ratio of the mass concentration of organism (COD) in the waste water be 1: 3, H
2O
2/ Fe
2+Mol ratio be 1: 2, oxidation pond pH is 3, settling bowl supernatant liquor pH is 7, the pH of dissolving tank is 0.3, and waste water is 1 hour in the flocculation basin residence time, and the oxidation pond residence time is 60 minutes, the settling bowl residence time is 2 hours, and the residence time of BAF is 4 hours.Result sees Table 1.Waste water is by after the catalytic oxidation treatment as can be seen from the data of table 1, and COD and oil-contg significantly reduce, and biodegradability significantly improves, and COD and the oil-contg through the BAF processed waste water further reduces again, satisfies the water quality requirement of qualified discharge.
Table 1 is handled not standard discharge waste water of refinery
| Project | COD/mg/L | Oil-contg/mg/L | B/C |
| Former water | 130 | 12 | 0.04 |
| The catalyzed oxidation water outlet | 80 | 2 | 0.31 |
| The BAF water outlet | 58 | 0.5 |
Embodiment 2
H is adopted in the pre-treatment of feed water by reverse osmosis in certain refinery's reusing sewage process
2O
2Be oxygenant, Fe
2SO
4Be catalyzer, used soda acid is dense H
2SO
4And NaOH.Operational condition is defined as: H
2O
2With the ratio of the mass concentration of organism (COD) in the waste water be 1: 2, H
2O
2/ Fe
2+Mol ratio is 1: 1, and oxidation pond pH is 5, and settling bowl supernatant liquor pH is 6.5, the pH of dissolving tank is 0.5, and waste water is 1 hour in the flocculation basin residence time, 40 minutes oxidation pond residence time, the settling bowl residence time is 1.5 hours, and the residence time of BAF is 3 hours.Waste water is by after the catalytic oxidation treatment as can be seen from the data of table 1, and COD significantly reduces, and biodegradability significantly improves, and the COD through the BAF processed waste water further reduces again, satisfies the into water quality requirement of reverse-osmosis treated.
The pre-treatment of table 2 feed water by reverse osmosis
| Project | COD/mg/L | B/C |
| Former water | 75 | 0.02 |
| The catalyzed oxidation water outlet | 45 | 0.33 |
| The BAF water outlet | 30 |
Embodiment 3
Handle not standard discharge waste water of certain chemical plant, the employing clorox is an oxygenant, Fe
2SO
4Be catalyzer, used soda acid is dense H
2SO
4And NaOH.Operational condition is: the ratio of the mass concentration of the organism in clorox and the waste water (COD) is 1: 3, clorox/Fe
2+Mol ratio be 1: 1.5, oxidation pond pH is 4, settling bowl supernatant liquor pH is 7.5, the pH of dissolving tank is 0.3, and waste water is 1 hour in the flocculation basin residence time, and the oxidation pond residence time is 60 minutes, the settling bowl residence time is 2 hours, and the residence time of BAF is 4 hours.Result sees Table 3.Waste water is by after the catalytic oxidation treatment as can be seen from the data of table 3, and COD and oil-contg significantly reduce, and biodegradability significantly improves, and COD and the oil-contg through the BAF processed waste water further reduces again, satisfies the water quality requirement of qualified discharge.
Table 3 is handled not standard discharge waste water of chemical plant
| Project | COD/mg/L | Oil-contg/mg/L | B/C |
| Former water | 120 | 11 | 0.03 |
| The catalyzed oxidation water outlet | 78 | 2 | 0.31 |
| The BAF water outlet | 57 | 0.6 |
Claims (16)
1. a catalyzed oxidation is united the method that BAF is handled waste water, may further comprise the steps in order:
1) makes pending waste water all or part of, enter oxidation pond through after flocculation basin carries out flocculation sediment;
2) add acid in oxidation pond, the pH value 0～6 of regulating waste water adds oxygenant and catalyzer and carries out catalytic oxidation;
3) waste water after the oxidation enters the settling bowl sedimentation, adds alkali after supernatant liquor is discharged and regulates pH value 6～9, enters BAF and handles the back discharge; The acidic precipitation that settles down is back in the dissolving tank, adds acid and is adjusted to all dissolvings of precipitation, and solution enters flocculation basin and all or part of pending waste water carries out flocculation precipitation reaction.
2. in accordance with the method for claim 1, it is characterized in that described oxygenant is selected from a kind of in hydrogen peroxide, ozone, hypochlorite, perchlorate, the persulphate.
3. according to claim 1 or 2 described methods, it is characterized in that described catalyzer is selected from goes back the ortho states transition metal ion.
4. in accordance with the method for claim 3, it is characterized in that described catalyzer is selected from Fe
2+, Mn
2+, Ni
2+, Co
2+, Cd
2+, Cu
2+, Ag
+, Cr
3+And Zn
2+In one or more.
5. in accordance with the method for claim 4, it is characterized in that described catalyst Fe
2+Derive from ferrous sulfate, iron protochloride, the Iron nitrate one or more.
6. in accordance with the method for claim 1, it is characterized in that the acid that is added is sulfuric acid, hydrochloric acid or nitric acid.
7. in accordance with the method for claim 1, it is characterized in that the alkali that is added is sodium hydroxide, potassium hydroxide, sodium bicarbonate or yellow soda ash.
8. in accordance with the method for claim 1, it is characterized in that also add coagulant aids in flocculation basin, the coagulant aids that is adopted is one or more in polymerize aluminum chloride, bodied ferric sulfate, the polyacrylamide.
9. in accordance with the method for claim 1, it is characterized in that the ratio of the mass concentration of the COD in oxygenant and the waste water is 5: 1～1: 100.
10. in accordance with the method for claim 1, it is characterized in that the ratio of the mass concentration of the COD in oxygenant and the waste water is 2: 1～1: 20.
11. in accordance with the method for claim 1, it is characterized in that the mol ratio of oxygenant and catalyzer is 10: 1～1: 3.
12. in accordance with the method for claim 1, it is characterized in that the mol ratio of oxygenant and catalyzer is 5: 1～1: 2.
13. in accordance with the method for claim 1, it is characterized in that the pH value of regulating waste water in the oxidation pond is 2～6.
14. in accordance with the method for claim 1, it is characterized in that the pH value of regulating the settling bowl supernatant liquor is 6～8.
15. in accordance with the method for claim 1, it is characterized in that the pH value is less than 2 in the adjusting dissolving tank.
16. in accordance with the method for claim 1, it is characterized in that, the residence time of waste water in oxidation pond can be 10-120 minute, and the residence time in settling tank can be 5～500 minutes, and the residence time in BAF can be 0.5～20 hour.
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|---|---|---|---|
| CN2009101807731A CN102040308B (en) | 2009-10-22 | 2009-10-22 | Method for treating wastewater by combining catalytic oxidation with biological aerated filter |
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2009
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