CN107055892B - Method for microwave-assisted catalytic oxidation of biochemical tail water of brewing wastewater by compounding of multiple metals - Google Patents
Method for microwave-assisted catalytic oxidation of biochemical tail water of brewing wastewater by compounding of multiple metals Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 239000002184 metal Substances 0.000 title claims description 9
- 150000002739 metals Chemical class 0.000 title claims description 8
- 238000013329 compounding Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- -1 nickel metal oxides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011514 vinification Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000013124 brewing process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000005855 radiation 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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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)
- Catalysts (AREA)
Abstract
The invention relates to a method for treating biochemical tail water of brewing wastewater by microwave-assisted catalytic oxidation of multiple metal compounds. The method has the advantages of strong pertinence, high reaction rate, stable treatment effect, strong operability and low operation cost. Provides technical support for upgrading, reconstruction and standard discharge of the brewhouse wastewater treatment.
Description
Technical Field
The invention relates to a method for treating brewing wastewater, in particular to a method for treating biochemical tail water of brewing wastewater by microwave-assisted catalytic oxidation of a compound of various metals.
Background
The brewing industry mostly adopts vinasse-compounded brewing, so that the brewing wastewater is particularly complex in water quality, large in water quality and water quantity fluctuation, contains a large amount of inorganic phosphorus, organic nitrogen and other substances, and belongs to organic wastewater which is poor in biodegradability, high in chroma and difficult to degrade. With the coming of the national fermentation alcohol and white spirit industrial water pollutant discharge standard (GB 27631-. The traditional metal catalyst has extremely strong oxidizing capability, but in practical application, the problems of high operation cost, single effect and the like occur.
Disclosure of Invention
The invention aims to provide a method for treating biochemical tail water of brewing wastewater by microwave-assisted catalytic oxidation compounded by various metals in order to improve the defects of the prior art. Effectively treating the sewage generated by the brewing process, efficiently reducing the pollution of chemical oxygen demand, total phosphorus and ammonia nitrogen to the environment, enabling the treated effluent to be clear, achieving the discharge standard and realizing the sustainable development of the brewing industry.
The technical scheme of the invention is as follows: a method for microwave-assisted catalytic oxidation of brewing wastewater biochemical tail water by compounding multiple metals comprises the following specific steps:
1) acidifying: acidifying the biochemical tail water of the brewing wastewater by using sulfuric acid, controlling the pH value of the wastewater, and carrying out acidification treatment;
2) oxidation treatment: adding an oxidant into the acidized effluent for oxidation reaction;
3) microwave treatment: treating the oxidation treatment effluent in a microwave reactor, adding a catalyst, and carrying out microwave reaction;
4) and (3) neutralization treatment: the effluent after microwave treatment enters a neutralization reaction tank, liquid caustic soda is added, the pH value of the wastewater is adjusted, and neutralization reaction is carried out;
5) and (3) precipitation treatment: and (5) entering a sedimentation tank, and standing.
Preferably, the pH value of the wastewater in the step 1) is controlled to be 3.0-4.0, and the acidification treatment time is 10-15 min.
Preferably, the oxidant in the step 2) is H2O2(ii) a Adding proportion is according to H2O2The ratio of the tail water to COD is 0.02-0.05: 1; the oxidation reaction time is 5-10 min.
Preferably, the catalyst in the step 3) is ceramsite loaded with metal oxides such as iron, manganese, nickel and the like; wherein the mass of the iron oxide loaded on the catalyst is 0.5-1.5% of the mass of the ceramsite, the mass of the manganese oxide is 0.3-1% of the mass of the ceramsite, and the mass of the nickel oxide is 0.1-0.5% of the mass of the ceramsite.
Preferably, the mass volume ratio of the catalyst to the wastewater in the step 3) is 10-20: 1 g/L;
preferably, the microwave power in the step 3) is 350-500W, and the microwave reaction time is 3-5 min.
Preferably, the pH value of the wastewater adjusted in the step 4) is 7.0-8.0; performing neutralization reaction for 5-10 min;
preferably, the standing time in the step 5) is 15-20 min.
Has the advantages that:
the microwave radiation catalyst can improve the thermal stability and the dispersity of the catalyst and enhance the reaction rate. The microwave-assisted catalytic oxidation technology is a novel wastewater treatment technology, combines microwaves and a catalyst compounded by various metals, utilizes the catalytic action of the microwaves, improves the reaction efficiency, and accelerates the oxidative degradation of pollutants;
the method of combining the catalyst compounded by various metals and microwaves is used for treating the biochemical tail water of the brewing wastewater, so that the stability of the effluent is ensured, the requirement of standard discharge is met for a long time, and the method has important significance on environmental protection in China;
COD, total phosphorus, ammonia nitrogen and chromaticity can be efficiently removed, the reaction rate is accelerated, and the effluent quality is stable; the metal compound catalyst taking the ceramsite as the carrier has pertinence to the brewing wastewater, improves the microwave utilization rate, enhances the treatment efficiency and reduces the operation cost; ensures that the brewing wastewater can meet the effluent quality of the discharge standard for a long time.
Drawings
FIG. 1 is a flow chart of the invention for treating biochemical tail water of brewing wastewater.
Detailed Description
The technical solution in the embodiment of the present invention will be clearly and completely described below with reference to fig. 1 in the embodiment of the present invention. Based on the embodiments of the present invention, other embodiments obtained by persons of ordinary skill in the art without any creative effort belong to the protection scope of the present invention.
Example 1
Advanced treatment method for wastewater of Sichuan brewing factory
The processing capacity of the embodiment of the invention is 1300m3And d, effluent COD, total phosphorus, ammonia nitrogen, chromaticity and the like of the wastewater after biochemical treatment do not reach the standard, and finally the effluent after treatment reaches the discharge standard of the wine making industry. The water quality of inlet water and outlet water is shown in Table 1.
The specific process comprises the following steps: firstly, using sulfuric acid to make acidification treatment of biochemical tail water of waste water treatment station of Sichuan's brewery, controlling pH value of waste water to be 3.0, making the acidified water after 15min undergo the process of oxidation treatment, and using H as oxidant2O2The adding proportion is according to H2O2The COD ratio of the biochemical tail water is 0.05: 1, after reacting for 10min, entering a microwave reactor for treatment, adding ceramsite loaded with iron, manganese and nickel metal oxides as a catalyst, and adding iron oxide on the catalystThe amount of the manganese oxide is 1.5 percent of the mass of the ceramsite, the mass of the manganese oxide is 0.3 percent of the mass of the ceramsite, the mass of the nickel oxide is 0.5 percent of the mass of the ceramsite, and the adding proportion is that the mass volume ratio of the catalyst to the wastewater is 20: 1g/L, adjusting the microwave power to 500W, reacting for 5min, feeding into a neutralization reaction tank, adding liquid alkali, adjusting the pH value of the wastewater to 7.0, reacting for 10min, feeding into a sedimentation tank, and standing for 20min to obtain the effluent.
TABLE 1 Water quality of inlet and outlet water of fermentation type brewing wastewater from Sichuan
Example 2
Method for treating wastewater of Guizhou certain brewhouse
The processing capacity of the embodiment of the invention is 510m3And d, the COD and the total phosphorus of the biochemical tail water are higher, the chroma exceeds the standard, and the finally treated effluent reaches the discharge standard of the wine making industry. The specific quality of the feed water is shown in Table 2.
Firstly, using sulfuric acid to make acidification treatment of biochemical tail water of brewing waste water, controlling pH value of waste water to be 4.0, making the acidified effluent water be undergone the process of oxidation treatment after 10min, using H as oxidant2O2The adding proportion is according to H2O2The COD ratio of the biochemical tail water is 0.02: 1, reacting for 5min, then treating in a microwave reactor, adding ceramsite loaded with iron, manganese and nickel metal oxides as a catalyst, wherein the mass of iron oxide on the catalyst is 0.5 percent of the mass of the ceramsite, the mass of manganese oxide is 0.3 percent of the mass of the ceramsite, the mass of nickel oxide is 0.5 percent of the mass of the ceramsite, and the adding proportion is that the mass-volume ratio of the catalyst to the wastewater is 10: 1g/L, adjusting the microwave power to 350W, reacting for 3min, then feeding into a neutralization reaction tank, adding liquid alkali, adjusting the pH value of the wastewater to 7.0, reacting for 5min, feeding into a sedimentation tank, and standing for 15 min.
TABLE 2 quality of inlet and outlet water of Maotai-flavor liquor-making wastewater in Guizhou of the present invention
Example 3
Advanced treatment method for wastewater of Jiangsu certain brewage
The treatment capacity of the embodiment of the invention is 850m3And d, effluent COD (chemical oxygen demand), total phosphorus, ammonia nitrogen, chromaticity and the like after treatment in a sewage plant do not reach the standard, and finally the effluent after treatment reaches the discharge standard of the wine making industry. The water quality of inlet water and outlet water is shown in Table 3.
The specific process comprises the following steps: firstly, using sulfuric acid to make acidification treatment of biochemical tail water of brewing waste water, controlling pH value of waste water to be 3.5, making the acidified water after 12min undergo the process of oxidation treatment, using H as oxidant2O2The adding proportion is according to H2O2The COD ratio of the biochemical tail water is 0.04: 1, reacting for 10min, then treating in a microwave reactor, adding ceramsite loaded with iron, manganese and nickel metal oxides as a catalyst, wherein the mass of iron oxide on the catalyst is 1.0 percent of the mass of the ceramsite, the mass of manganese oxide is 1.0 percent of the mass of the ceramsite, the mass of nickel oxide is 0.2 percent of the mass of the ceramsite, and the adding proportion is that the mass-volume ratio of the catalyst to the wastewater is 13: 1g/L, adjusting the microwave power to 400W, reacting for 5min, then feeding the wastewater into a neutralization reaction tank, adding liquid alkali, adjusting the pH value of the wastewater to 7.8, reacting for 8min, feeding the wastewater into a sedimentation tank, and standing for 18min to obtain the effluent.
TABLE 3 Water quality of inlet and outlet water of fermentation type brewing wastewater of Jiangsu
Claims (6)
1. A method for microwave-assisted catalytic oxidation of brewing wastewater biochemical tail water by compounding multiple metals comprises the following specific steps:
1) acidifying: acidifying the biochemical tail water of the brewing wastewater by using sulfuric acid, controlling the pH value of the wastewater, and carrying out acidification treatment;
2) oxidation treatment: adding an oxidant into the acidized effluent for oxidation reaction;
3) microwave treatment: treating the oxidation treatment effluent in a microwave reactor, adding a catalyst, and carrying out microwave reaction; wherein the catalyst is ceramsite loaded with metal oxides of iron, manganese and nickel; wherein the mass of the iron oxide loaded on the catalyst is 0.5-1.5% of the mass of the ceramsite, the mass of the manganese oxide is 0.3-1% of the mass of the ceramsite, and the mass of the nickel oxide is 0.1-0.5% of the mass of the ceramsite; the mass-volume ratio of the catalyst to the wastewater is 10-20: 1 g/L;
4) and (3) neutralization treatment: the effluent after microwave treatment enters a neutralization reaction tank, liquid caustic soda is added, the pH value of the wastewater is adjusted, and neutralization reaction is carried out;
5) and (3) precipitation treatment: and (5) entering a sedimentation tank, and standing.
2. The method according to claim 1, characterized in that the pH value of the wastewater in the step 1) is controlled to be 3.0-4.0, and the acidification treatment time is 10-15 min.
3. The process according to claim 1, characterized in that the oxidizing agent of step 2) is H2O2(ii) a Adding proportion is according to H2O2The ratio of the tail water to COD is 0.02-0.05: 1; the oxidation reaction time is 5-10 min.
4. The method according to claim 1, wherein the microwave power in step 3) is 350-500W, and the microwave reaction time is 3-5 min.
5. The method according to claim 1, characterized in that the pH value of the wastewater adjusted in the step 4) is 7.0-8.0; and (5) carrying out neutralization reaction for 5-10 min.
6. The method according to claim 1, wherein the standing time in the step 5) is 15-20 min.
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| CN108083521A (en) * | 2017-12-12 | 2018-05-29 | 中海油天津化工研究设计院有限公司 | A kind of method that integrated micro oxidation reduces organic wastewater TOC |
| CN109019753B (en) * | 2018-07-11 | 2021-08-31 | 广州机械设计研究所 | Method for treating organic wastewater by circulating sequencing batch microwave catalytic oxidation |
| CN108996654B (en) * | 2018-07-11 | 2021-07-20 | 广州机械设计研究所 | Microwave catalytic oxidation organic wastewater treatment equipment |
| CN114230049B (en) * | 2021-12-31 | 2023-03-17 | 贵州筑信水务环境产业有限公司 | Pretreatment system for white spirit brewing wastewater catalytic oxidation coupling neutralization precipitation and application |
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| CN1544360A (en) * | 2003-11-13 | 2004-11-10 | 哈尔滨工业大学 | Multi-phase concentration, microwave synergy, catalytic oxidation method for degrading organic pollutant in water |
| CN101423261A (en) * | 2007-10-30 | 2009-05-06 | 同济大学 | Method and device for degradation of contaminant by microwave reinforcement catalytic wet-type oxidation |
| CN103159282A (en) * | 2012-12-25 | 2013-06-19 | 湘潭大学 | Method for catalyzing and degrading phenolic wastewater through microwaves |
| CN104291506A (en) * | 2014-09-18 | 2015-01-21 | 中国海洋石油总公司 | Method for treating rubber chemical wastewater by microwave enhanced microelectrolysis combined oxidation |
| CN105800727A (en) * | 2016-04-29 | 2016-07-27 | 东莞市绿月环保工程有限公司 | Microwave catalysis oxidation water treatment device |
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| DK96392D0 (en) * | 1992-07-27 | 1992-07-27 | Risoe Forskningscenter | MODIFICATION METHOD |
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|---|---|---|---|---|
| CN1544360A (en) * | 2003-11-13 | 2004-11-10 | 哈尔滨工业大学 | Multi-phase concentration, microwave synergy, catalytic oxidation method for degrading organic pollutant in water |
| CN101423261A (en) * | 2007-10-30 | 2009-05-06 | 同济大学 | Method and device for degradation of contaminant by microwave reinforcement catalytic wet-type oxidation |
| CN103159282A (en) * | 2012-12-25 | 2013-06-19 | 湘潭大学 | Method for catalyzing and degrading phenolic wastewater through microwaves |
| CN104291506A (en) * | 2014-09-18 | 2015-01-21 | 中国海洋石油总公司 | Method for treating rubber chemical wastewater by microwave enhanced microelectrolysis combined oxidation |
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