CN114291943A - Process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis - Google Patents
Process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis Download PDFInfo
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 49
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 title claims abstract description 47
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- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
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Abstract
The invention provides a process for treating benzohydroxamic acid production wastewater by ozone iron-carbon micro-electrolysis, which comprises the following steps: s01, introducing ozone into the benzohydroxamic acid production wastewater, and continuously carrying out an ozone reaction; s02, adding a hydrogen peroxide and iron-carbon mixed reagent, uniformly stirring, and continuously carrying out iron-carbon micro-electrolysis reaction; s03, adding a calcium hydroxide solution to adjust the pH value, and then continuously aerating; s04, standing and settling to precipitate ferrous hydroxide and ferric hydroxide obtained by iron-carbon micro-electrolysis reaction. The invention completes high-efficiency wastewater treatment by ozone + iron-carbon micro-electrolysis reaction and optimal test data research.
Description
Technical Field
The invention relates to the field of water treatment processes, and particularly relates to a process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis.
Background
The water environment pollution brings great challenges to water supply treatment and poses great threats to urban safe water supply. With the development and progress of economic society, the demand of industrial production on mineral products is continuously expanded, so that the mining industry is developed vigorously, wherein the benzohydroxamic acid is a relatively common mineral separation agent and belongs to refractory organic matters.
The production wastewater of the benzohydroxamic acid is organic wastewater with strong acidity, pungent smell and high COD content. The biological carrier is directly discharged into the natural environment, can be enriched and accumulated in the water body, soil and other environments, thereby causing the pollution of the water body and the soil, and can be accumulated in organisms after being ingested by the organisms to generate physiological toxicity. Therefore, the method for treating the benzohydroxamic acid production wastewater quickly and effectively has great significance.
At present, the research on treating hydroximic acid by a biochemical method is less, and the research on mineral processing industrial wastewater containing hydroximic acid collecting agents is less. The research of treating industrial waste water includes physical and chemical process, biochemical process, advanced treatment, advanced oxidation technology, etc. However, in actual industrial production, the components of the beneficiation reagent wastewater are different, the difficulty of wastewater treatment is greatly increased, and the complete removal of organic substances in water is difficult to ensure by a single process.
It is obvious that the prior art has certain defects.
Disclosure of Invention
The invention aims to solve the technical problem of providing a process for treating wastewater produced by benzohydroxamic acid through ozone iron-carbon micro-electrolysis, and completing efficient wastewater treatment through ozone and iron-carbon micro-electrolysis reaction and optimal test data research.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis comprises the following steps:
s01, introducing ozone into the benzohydroxamic acid production wastewater, and continuously carrying out an ozone reaction;
s02, adding a hydrogen peroxide and iron-carbon mixed reagent, uniformly stirring, and continuously carrying out iron-carbon micro-electrolysis reaction;
s03, adding a calcium hydroxide solution to adjust the pH value, and then continuously aerating;
s04, standing and settling to precipitate ferrous hydroxide and ferric hydroxide obtained by iron-carbon micro-electrolysis reaction.
Further, in the step S01, the ozone reaction time is 60-120 min.
Further, in step S01, the ozone is added in an amount of: each liter of the benzohydroxamic acid production wastewater corresponds to 6 g/h.
Further, in step S02, the amount of hydrogen peroxide added is: each liter of the benzohydroxamic acid production wastewater corresponds to 12ml of hydrogen peroxide.
Further, in step S02, the ratio of iron to carbon is 1: 3.
Further, in step S02, the amount of iron carbon added is: each liter of the benzohydroxamic acid production wastewater corresponds to 160g of iron carbon.
Further, in the step S02, the iron-carbon micro-electrolysis reaction time is 1 h.
Further, in step S03, a calcium hydroxide solution is added to adjust the PH to 7.
Further, in the step S03, the aeration time is 30-60 min.
Further, in the step S04, the settling time is 4 h.
The process for treating the production wastewater of the benzohydroxamic acid by ozone iron-carbon micro-electrolysis has the following advantages:
through the ozone and iron-carbon micro-electrolysis combined process, the benzohydroxamic acid production wastewater is efficiently treated, and the effect is better than that of a single treatment process. All process data are tested through experiments to obtain optimal parameters, and the COD removal rate is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Referring to fig. 1, the embodiment of the present invention provides a process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis, which is directed to the treatment of production wastewater of benzohydroxamic acid, and specifically comprises the following steps:
s01, introducing ozone into the benzohydroxamic acid production wastewater, and continuously carrying out an ozone reaction;
s02, adding a hydrogen peroxide and iron-carbon mixed reagent, uniformly stirring, and continuously carrying out iron-carbon micro-electrolysis reaction;
s03, adding a calcium hydroxide solution to adjust the pH value, and then continuously aerating;
s04, standing and settling to precipitate ferrous hydroxide and ferric hydroxide obtained by iron-carbon micro-electrolysis reaction.
The process features that the combined treatment process of ozone and then iron-carbon micro-electrolysis is used. The process principle is as follows:
ozone advanced oxidation mechanism:
ozone is an oxidant with extremely strong oxidizability, and is directly reacted through oxidizability, and is in contact oxidation reaction in a solution with higher pH to generate hydroxyl radicals, so that organic matters are degraded by utilizing the oxidation effect of the hydroxyl radicals. Ozone is more oxidizing than chlorine and is able to permeate cell membranes, inactivate nucleic acids and proteins inside the cells, kill bacteria in the water, and oxidize to remove organic contaminants from the water.
Ozone can be used for treating various pollutants in water by virtue of the super-strong oxidizing ability of the ozone, particularly difficultly biodegradable organic pollutants, and can achieve a better treatment effect. Since only a small amount of hydroxyl radicals are generated under the O3 treatment alone, the generation of more hydroxyl radicals can be excited only by the coordination with other physical catalysis or chemical methods. Wherein, under the catalysis of ferrous ions and ferric ions, ozone can be decomposed to generate more hydroxyl radicals. The principle is as follows:
O3+OH-→.O2+.HO2
O3+.HO2→2O2+.OH
Fe2++O3→Fe3++.O3 -
H++.O3 -→O2+.OH
Fe2++O3→FeO2++O2
FeO2++HO2→Fe3++.OH+OH-
iron-carbon microelectrolysis principle:
the iron-carbon micro-electrolysis can perform oxidation-reduction reaction in the wastewater, and organic pollutants which are difficult to degrade in the wastewater are degraded under the action of ferrous ions and hydrogen atoms; simultaneously, ferrous ion and ferric ion can form ferrous hydroxide and ferric hydroxide deposit and play the coagulation action, destabilizes suspended solid and organic matter in the waste water, and the coagulation becomes the flocculating constituent, thereby the organic matter obtains getting rid of, and the concrete principle is as follows:
(1) electrochemical action: the main effect of the electrochemical reaction on the wastewater is that the electrode reaction formula is as follows:
anode reaction under oxygen-free condition:
Fe-2eFe→Fe2+
cathode reaction in the absence of oxygen:
2H++2e→H2
anode reaction in aerobic condition:
Fe-2eFe→Fe2+
cathode reaction in aerobic condition:
O2+4H++4e→2H2o (acid condition)
O2+2H2O+4e→4OH-(neutral or alkaline conditions)
From the above-mentioned iron-carbon electrode reaction formula, it is known that iron-carbon is the fastest to cause electrochemical corrosion under acidic aerobic conditions, and the effect of treating wastewater is the best.
(2) Reduction: after electrode reaction, the solution has high activity of atomic H and nascent state ferrous ion, which can break and open the ring of organic matter to degrade the organic matter.
(3) Oxidation: during the electrochemical reaction, free radicals can be generated, so that organic matters are oxidized and removed.
(4) Coagulation: the iron of positive pole loses two electrons, generates ferrous ion, under aerobic and alkaline condition, can turn into ferrous hydroxide and ferric hydroxide sediment, and it can adsorb the organic matter, becomes the flocculating constituent and subsides, and the organic matter can get rid of, and the reaction sequence is:
Fe2++2OH-＝Fe(OH)2↓
4Fe2++8OH-+O2+2H2O＝4Fe(OH)2↓
research shows that the treatment effect of the ozone and iron-carbon micro-electrolysis combined process is better than that of the iron-carbon micro-electrolysis and ozone combined process. The reason is that if the iron-carbon micro-electrolysis reaction is performed before, organic matters which are easy to degrade in the wastewater are removed firstly after the iron-carbon micro-electrolysis, and in the subsequent ozone reaction, although iron ions after the iron-carbon micro-electrolysis reaction can catalyze ozone oxidation, most of the remaining organic matters in the wastewater are difficult to degrade, and the effect of ferric hydroxide coagulation precipitation is avoided, so that the capability of ozone oxidation of the organic matters is reduced. Therefore, the ozone oxidation reaction is advanced.
Preferably, in the step S01, the ozone reaction time is 60-120 min. Research shows that the degradation rate of organic matters in the benzohydroxamic acid wastewater is in positive correlation with the reaction time of ozone, and when the reaction time is less than 60min, the degradation rate of the organic matters is obviously accelerated along with the increase of the reaction time of the ozone; when the reaction time exceeds 60min, the increase of the degradation rate of the organic matter is slowed down. The optimum reaction time for the ozone reaction is 60min in view of the problem of treatment efficiency.
Preferably, in step S01, the ozone is added in an amount of: each liter of the benzohydroxamic acid production wastewater corresponds to 6 g/h. Research shows that due to the increase of the adding amount of ozone, macromolecular organic matters in the wastewater generated in the production of the benzohydroxamic acid are rapidly, effectively and thoroughly decomposed.
Preferably, in step S02, the amount of hydrogen peroxide added is: each liter of the benzohydroxamic acid production wastewater corresponds to 12ml of hydrogen peroxide. Studies have shown that the rate of organic degradation is greatly reduced when hydrogen peroxide is added in excess of or below 12 ml. Because ferrous ions in the water body can serve as a catalyst after iron-carbon micro-electrolysis, the hydrogen peroxide generates hydroxyl radicals, the oxidation performance of the hydrogen peroxide is improved, and the treatment effect is improved; however, when the amount of the added hydrogen peroxide is too large, the excessive hydrogen peroxide is decomposed by itself and reacts with hydroxyl radicals, so that the content of the hydroxyl radicals is reduced, and the reaction for oxidizing organic substances is weakened.
Preferably, in step S02, the ratio of iron to carbon is 1: 3. Research shows that when iron is more than carbon, the degradation rate of organic matters is reduced, iron-carbon micro-electrolysis is easy to harden and passivate during reaction, and the COD degradation effect is not obvious. When the carbon is more than that of the iron, and the iron-carbon ratio is 1: and 3, the organic matter degradation rate is fastest, and the COD removal rate is highest.
Preferably, in step S02, the amount of iron carbon added is: each liter of the benzohydroxamic acid production wastewater corresponds to 160g of iron carbon. Research shows that when the content of iron and carbon is too high, iron oxide aggregation can be caused, so that the contact area between the activated carbon and iron is reduced, and the treatment effect is influenced.
Preferably, in step S02, the iron-carbon micro-electrolysis reaction time is 1 h. Research shows that when the iron-carbon micro-electrolysis reaction time exceeds 1h, the degradation rate of organic matters in the benzohydroxamic acid production wastewater is sharply reduced and then increased and decreased, but the COD removal rate is far higher than that when the iron-carbon micro-electrolysis reaction time is 1 h. This is because sufficient electrons are not obtained in the initial stage of the reaction to reduce the production wastewater of benzohydroxamic acid, and when the reaction is continuously carried out, the electrons in water begin to satisfy the requirement that the production wastewater of benzohydroxamic acid undergoes the reduction reaction, however, the longer the reaction time is, the more the iron surface is oxidized and passivated, thereby affecting the reduction reaction.
Preferably, in step S03, a calcium hydroxide solution is added to adjust the PH to 7. Research shows that when the pH value of the reaction of iron-carbon micro-electrolysis and the production wastewater of the benzohydroxamic acid is acidic, the potential difference of the iron-carbon micro primary battery is large, the oxidation-reduction potential is also increased, the dissolution of iron is facilitated, a large amount of ferrous ions and reduced hydrogen are generated, and the reaction rate is accelerated. When the pH value is 7, the iron-carbon micro-electrolysis fully plays the coagulation role of ferrous ions and ferric ions, the degradation rate of organic matters is fastest, and the removal rate of COD is highest.
Preferably, in the step S03, the aeration time is 30-60 min. Research shows that when the aeration time is 30-60min, the organic matter degradation rate is the largest, the COD removal rate is the highest, and the organic matter degradation rate and the COD removal rate are all basically equal. The optimal aeration time is 30min, considering the reaction efficiency and the effective contact area of iron carbon and organic pollutants is prevented by the aerated bubbles.
Preferably, in step S04, the settling time is 4 h. Research shows that the optimal settling time is 4 hours because the time for removing organic matters through net capture and rolling sweeping of ferrous hydroxide and ferric hydroxide flocculation precipitation formed by hydrolyzing ferrous ions and ferric ions produced after the production wastewater of the benzohydroxamic acid and the iron-carbon are subjected to micro-electrolysis is required.
The invention provides a process for treating production wastewater of benzohydroxamic acid by ozone iron-carbon micro-electrolysis, which treats the production wastewater of the benzohydroxamic acid by an ozone and iron-carbon micro-electrolysis composite treatment process. And through detailed research and analysis of each experimental data, optimal process data are obtained, and efficient treatment of the production wastewater of the benzohydroxamic acid is realized.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A process for treating wastewater produced by benzohydroxamic acid through ozone iron-carbon micro-electrolysis is characterized by comprising the following steps:
s01, introducing ozone into the benzohydroxamic acid production wastewater, and continuously carrying out an ozone reaction;
s02, adding a hydrogen peroxide and iron-carbon mixed reagent, uniformly stirring, and continuously carrying out iron-carbon micro-electrolysis reaction;
s03, adding a calcium hydroxide solution to adjust the pH value, and then continuously aerating;
s04, standing and settling to precipitate ferrous hydroxide and ferric hydroxide obtained by iron-carbon micro-electrolysis reaction.
2. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 1, wherein the process comprises the following steps: in the step S01, the ozone reaction time is 60-120 min.
3. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 2, wherein the process comprises the following steps: in step S01, the amount of ozone added is: each liter of the benzohydroxamic acid production wastewater corresponds to 6 g/h.
4. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 1, wherein the process comprises the following steps: in step S02, the amount of hydrogen peroxide added is: each liter of the benzohydroxamic acid production wastewater corresponds to 12ml of hydrogen peroxide.
5. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 1, wherein the process comprises the following steps: in step S02, the iron-carbon ratio is 1: 3.
6. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 5, wherein the process comprises the following steps: in step S02, the amount of iron carbon added is: each liter of the benzohydroxamic acid production wastewater corresponds to 160g of iron carbon.
7. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 4, 5 or 6, wherein: in the step S02, the iron-carbon micro-electrolysis reaction time is 1 h.
8. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 1, wherein the process comprises the following steps: in step S03, a calcium hydroxide solution is added to adjust the PH to 7.
9. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 8, wherein the process comprises the following steps: in the step S03, the aeration time is 30-60 min.
10. The process for treating wastewater from production of benzohydroxamic acid by ozone iron-carbon micro-electrolysis according to claim 1, wherein the process comprises the following steps: in the step S04, the settling time is 4 h.
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| Title |
|---|
| 方俊华;刘兰;穆军伟;: "铁碳微电解-Fenton法预处理苯胺基乙腈生产废水" * |
| 王辉;陈金元;: "有机硅树脂生产废水微电解预处理工艺研究" * |
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