CN111675305A - Organic wastewater oxidation treatment method and application thereof - Google Patents
Organic wastewater oxidation treatment method and application thereof Download PDFInfo
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- CN111675305A CN111675305A CN202010540263.7A CN202010540263A CN111675305A CN 111675305 A CN111675305 A CN 111675305A CN 202010540263 A CN202010540263 A CN 202010540263A CN 111675305 A CN111675305 A CN 111675305A
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Abstract
The invention provides an organic wastewater oxidation treatment method and application thereof, relating to the technical field of sewage treatment, wherein the treatment method comprises the steps of adding elementary substance iron, ferrous ions and persulfate into organic wastewater for treatment; in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50-100, the method effectively avoids the problem of overlarge initial ferrous ion concentration in the treatment process; meanwhile, the long-acting stable existence of ferrous ions as an activating agent in a reaction system can be kept; in addition, the oxidation system formed by the simple substance iron, the ferrous ions and the persulfate according to the specific molar ratio can also maintain the relative stability of the concentration of sulfate radicals, and the problem of reaction failure caused by the fact that the proportion of the ferrous ions and the persulfate is difficult to adjust when the existing ferrous ions are used for activating the persulfate to treat the organic polluted wastewater is solved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an organic wastewater oxidation treatment method and application thereof.
Background
In recent years, ecological environment protection, treatment and restoration are concerned, and particularly, water pollution treatment is the most urgent. The COD value is "chemical oxygen demand", which represents the amount of oxygen required by potassium dichromate to oxidize one liter of organic matter in the wastewater under strongly acidic conditions, and may approximately represent the amount of organic matter in the wastewater. The water quality monitoring method is a basic comprehensive index for water quality monitoring, and the higher the COD value in the water body is, the more serious the organic matter pollution is, the more easily the water body balance is damaged, the further the surrounding environment is influenced, and the health of human is seriously harmed; if the nitrogen with high concentration is contained, the water body can be eutrophicated, the algae can be propagated in a large quantity, the content of dissolved oxygen in the water is reduced, and aquatic animals die in a large quantity, so that the sewage treatment significance is great.
Common sewage treatment methods include physical adsorption, biodegradation, chemical methods and combined application. The physical adsorption method does not solve the problems from the source, the adsorption efficiency is relatively poor, and certain problems exist in the analytic regeneration. The biological method has wide application, but has longer period and higher cost, and has difficulty for a system with low BOD value and high salinity; the chemical oxidation method is generally an air oxidation method, a wet oxidation method, an advanced oxidation method, or the like. The Fenton-like reaction-persulfate activation technology in the advanced oxidation method can form sulfate radicals, has high electrode potential and long free radical service life, can exist in an environment with pH less than 8, and has certain application potential in the degradation of organic pollutants. Ferrous ions are widely used as an activating agent for persulfate activation due to the advantages of wide sources, low price, no toxic action on the environment of ferric iron generated after reaction, easy reducibility and utilization by a reducing agent and the like.
However, in a treatment system for treating organic polluted wastewater by singly using ferrous ions to activate persulfate, the ratio of the ferrous ions to persulfate is difficult to adjust, and when the initial concentration of the ferrous ions in a solution is too high and is easy to directly react with generated sulfate radicals, the sulfate radicals are subjected to side reaction, and the ferrous ions as an activator are also quickly inactivated; when the initial concentration of ferrous ions in the solution is too low, the activation capability is reduced, and the generated low-concentration sulfate radicals can not well degrade organic pollutants.
Therefore, researches and developments on an organic wastewater oxidation treatment method are necessary and urgent to further solve the problem that reaction failure is caused by the fact that the proportion of ferrous ions and persulfate is difficult to adjust when the existing method singly uses ferrous ions to activate persulfate to treat organic polluted wastewater.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an organic wastewater oxidation treatment method, which comprises the steps of adding elementary substance iron, ferrous ions and persulfate into organic wastewater for treatment; the components are regulated according to a specific molar ratio in the treatment process, so that the generation rate and the concentration of sulfate radical in a persulfate reaction system can be stably activated, the long-acting existence of ferrous ions as an activating agent is ensured, and the problem of reaction failure caused by the fact that the proportion of ferrous ions and persulfate is difficult to regulate when the existing persulfate is singly used for activating persulfate to treat organic polluted wastewater is effectively avoided.
The second purpose of the invention is to provide an application of the organic wastewater oxidation treatment method in the field of organic pollutant-containing wastewater treatment.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an organic wastewater oxidation treatment method, which comprises the steps of adding elementary substance iron, ferrous ions and persulfate into organic wastewater for treatment;
in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50 to 100.
Further, in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50-100 parts;
preferably, the molar ratio of the elementary substance iron to the ferrous ions to the persulfate is 1-10: 0.2-5: 50-85;
more preferably, the molar ratio of the elementary iron to the ferrous ions to the persulfate is 1-5: 0.1-1: 50-70.
Further, the simple substance iron is iron powder;
preferably, the particle size of the iron powder is 0.5-1000 μm, and preferably 150-500 μm.
Further, the ferrous iron source of the ferrous ions comprises at least one of ferrous sulfate heptahydrate, ferrous acetate and ferrous chloride tetrahydrate;
preferably, the ferrous iron source of ferrous ions comprises ferrous sulfate heptahydrate.
Further, the persulfate includes at least one of sodium persulfate, potassium persulfate, and ammonium persulfate;
preferably, the persulfate salt comprises sodium persulfate and/or potassium persulfate.
The invention provides an application of the organic wastewater oxidation treatment method in organic pollutant-containing wastewater treatment;
preferably, the organic pollutant-containing wastewater is printing and dyeing wastewater with a COD value of between 1000 and 2000.
Further, the reaction conditions of the application at least satisfy at least one of the following:
the reaction pH value is 2-6, the reaction temperature is 15-70 ℃, and the reaction time is 10-50 min;
preferably, the reaction conditions of the application at least satisfy at least one of the following:
the reaction pH value is 3-5, the reaction temperature is 15-50 ℃, and the reaction time is 20-40 min.
Further, the processing method of the application comprises the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the organic pollutant-containing wastewater to be treated, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 0.5-20: 0.1-10: 50-100 parts;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 2-6, and then reacting at the temperature of 15-70 ℃ for 10-50min to complete the treatment;
preferably, the processing method of the application comprises the following steps:
(a) adding simple substance iron, ferrous ions and persulfate into the wastewater containing organic pollutants to be treated, and adjusting the molar ratio of the simple substance iron to the ferrous ions to the persulfate to be 1-5: 0.1-1: 50-70;
(b) and (c) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 3-5, and then reacting at the temperature of 15-50 ℃ for 20-40 min to complete the treatment.
Further, the reaction method of the reaction in the step (b) comprises one or a combination of more of standing, stirring, shaking and ultrasound.
Furthermore, when the reaction is oscillation, the oscillation rate is 200-250 rpm, preferably 210 rpm;
preferably, when the reaction is ultrasonic, the power of the ultrasonic is 30-60W, and preferably 40W.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an organic wastewater oxidation treatment method, which comprises the steps of adding elementary substance iron, ferrous ions and persulfate into organic wastewater for treatment; in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50 to 100. In the oxidation treatment system, the simple substance iron, the ferrous ions and the persulfate are regulated by a specific molar ratio, so that the problem of overlarge initial ferrous ion concentration is effectively avoided; meanwhile, by introducing simple substance iron, when the concentration of ferrous ions in the reaction system is insufficient, ferrous ions (namely Fe) are generated by the reaction of the simple substance iron and ferric iron0+2Fe3+＝3Fe2+) And the simple substance iron and the persulfate are dissolved in water to generate hydrogen ions (namely Fe + 2H)+＝Fe2++H2) Continuous Fe supplement2+So as to further keep the long-acting stable existence of ferrous ions as an activating agent in a reaction system; further, persulfate is as SO4 -Precursor, (S)2O8 2-+Fe2+＝·SO4 -+SO4 2-+Fe3+) Its concentration and Fe2+The concentration affects the rate and concentration of free radicals produced, and thus the decomposition of contaminants. The oxidation system consisting of the elementary iron, the ferrous ions and the persulfate through a specific molar ratio can also maintain the relative stability of the concentration of the sulfate radical. Therefore, the organic wastewater oxidation treatment method can stabilize the generation rate and concentration of sulfate radical in the activated persulfate reaction system, ensure the long-acting existence of activating agent ferrous ions, and effectively avoid the problem of reaction failure caused by the difficulty in adjusting the ratio of ferrous ions to persulfate radical when the existing persulfate activated by ferrous ions is used alone to treat organic polluted wastewater.
The method for oxidizing and treating the organic wastewater provided by the invention can be widely applied to the field of treatment of wastewater containing organic pollutants.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic reaction flow diagram of an organic wastewater oxidation treatment method provided by the invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
According to one aspect of the invention, an organic wastewater oxidation treatment method comprises the steps of adding elemental iron, ferrous ions and persulfate into organic wastewater for treatment;
in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50 to 100.
The invention provides an organic wastewater oxidation treatment method, which comprises the steps of adding elementary substance iron, ferrous ions and persulfate into organic wastewater for treatment; in the treatment process, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50 to 100. In the oxidation treatment system, the simple substance iron, the ferrous ions and the persulfate are regulated by a specific molar ratio, so that the problem of overlarge initial ferrous ion concentration is effectively avoided; meanwhile, by introducing simple substance iron, when the concentration of ferrous ions in the reaction system is insufficient, ferrous ions (namely Fe) are generated by the reaction of the simple substance iron and ferric iron0+2Fe3+＝3Fe2+) And the simple substance iron and the persulfate are dissolved in water to generate hydrogen ions (namely Fe + 2H)+＝Fe2++H2) Continuous Fe supplement2+So as to further keep the long-acting stable existence of ferrous ions as an activating agent in a reaction system; further, persulfate is as SO4 -Precursor, (S)2O8 2-+Fe2+＝·SO4 -+SO4 2-+Fe3+) Its concentration and Fe2+The concentration affects the rate and concentration of free radicals produced, and thus the decomposition of contaminants. The oxidation system consisting of the elementary iron, the ferrous ions and the persulfate through a specific molar ratio can also maintain the relative stability of the concentration of the sulfate radical. Therefore, the method for the oxidation treatment of the organic wastewater can stably activate the persulfate reaction systemThe generation rate and concentration of sulfate radical free radicals, and the long-acting existence of ferrous ions of an activating agent is ensured, so that the problem of reaction failure caused by the fact that the proportion of ferrous ions and persulfate is difficult to adjust when the existing ferrous ions are used for activating persulfate to treat organic polluted wastewater independently is effectively solved.
FIG. 1 is a schematic diagram of the reaction flow of the organic wastewater oxidation treatment method, as shown in FIG. 1:
wherein, the reaction formulas of (1) to (5) in fig. 1 are:
(1)Fe2+-e-→Fe3+
(2)S2O8 2-+e-→SO4 2-+SO4 -·
(1)+(2)
(3)2Fe3++Fe0→3Fe2+
(4)2H++Fe0→2Fe2++H2
(5)
in a preferred embodiment of the invention, in the treatment process, the molar ratio of the elemental iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50-100;
in the preferred embodiment, the molar ratio of the elementary substance iron to the ferrous ions to the persulfate is 1-10: 0.2-5: 50-85;
as a preferable embodiment, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 1-10: 0.2-5: 50-85, under the condition of the molar ratio, the good degradation effect is achieved on COD in the organic pollutant wastewater, the degradation effect of the organic pollutant is affected by excessively high concentration of the simple substance iron or excessively high concentration of the ferrous ions, and the oxidation treatment system has a wide application prospect in the aspect of degradation of high-concentration low-Biochemical Oxygen Demand (BOD) pollutants in the printing and dyeing wastewater in the actual operation process.
Preferably, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 1-5: 0.1-1: 50-70.
In a preferred embodiment of the present invention, the elemental iron is iron powder;
as a preferred embodiment, the elementary iron is iron powder, which can be more favorable for the reaction of the elementary iron with other components in the reaction system.
In the preferred embodiment, the particle size of the iron powder is 0.5 to 1000 μm, preferably 150 to 500 μm.
In a preferred embodiment, the particle size of the iron powder is 150 to 500 μm, and if the particle size of the iron powder is too small and the reactivity is too high, the Fe can be rapidly increased2+Instead, the sulfate radicals are brought into contact with Fe2+Side reactions occur, which are unfavorable for the main degradation reaction of organic matters; the iron powder has too large particle size, too small specific surface area and very low reaction activity, and can not realize the reactivation of Fe2+And auxiliary activation of S2O8 2-And (4) acting.
In a preferred embodiment of the present invention, the ferrous iron source of ferrous ions comprises at least one of ferrous sulfate heptahydrate, ferrous acetate, and ferrous chloride tetrahydrate;
preferably, the ferrous iron source of ferrous ions is ferrous sulfate heptahydrate. Ferrous chloride forms chloride anions in the system, and easily influences the COD determination.
In a preferred embodiment of the present invention, the persulfate includes at least one of sodium persulfate, potassium persulfate, and ammonium persulfate;
preferably, the persulfate salt comprises sodium persulfate and/or potassium persulfate.
According to one aspect of the invention, the application of the organic wastewater oxidation treatment method in the treatment of wastewater containing organic pollutants;
the method for oxidizing and treating the organic wastewater provided by the invention can be widely applied to the field of treatment of wastewater containing organic pollutants.
In a preferred embodiment of the present invention, the organic pollutant-containing wastewater is printing and dyeing wastewater with a COD value of 1000 to 2000, and the absorbance values at different wavelengths are respectively: a. the436＝0.523， A525＝0.453，A620＝0.638。
In a preferred embodiment of the present invention, the reaction conditions applied at least satisfy at least one of the following:
the reaction pH value is 2-6, the reaction temperature is 15-70 ℃, and the reaction time is 10-50 min;
as a preferred embodiment, the reaction pH is 2 to 6, and the pH control during the application process mainly includes the following aspects: 1) influencing the activator Fe2+At a high pH, Fe2+Will be Fe (OH)2Form exists and will be oxidized relatively quickly to Fe (OH)3To be inactivated; 2) influencing Fe2+At a lower pH, a higher concentration of H+Faster reaction rate with Fe, Fe2+The amount of replenishment is also larger. 3) The reactivation speed is influenced, the metal ion hydrolysis degree is deepened along with the increase of pH, the reactivation difficulty is increased, and the speed is slowed down. 4) The existence state of the sulfate radical is influenced, and the sulfate radical is partially converted into hydroxyl radical with shorter service life and relatively poorer oxidizing capability at high pH.
In a preferred embodiment, the reaction temperature is 15 to 70 ℃ and a moderate increase in temperature (for example, 60 to 70 ℃) increases the degradation efficiency and deepens the degradation degree, but the energy input is increased and the economical efficiency of the application is poor.
As a preferred embodiment, the degradation can be completed within 10-50min of reaction time, so that the degradation efficiency is improved, the operation time is saved, and other degradation methods in the prior art can complete the degradation within 2-3h, even 7-8h, so that the degradation method provided by the invention has the advantages of high degradation efficiency, good degradation effect and the like.
Typical but non-limiting preferred embodiments of the above reaction pH are: 2. 3, 4, 5 and 6; typical but non-limiting preferred embodiments of the above reaction temperatures are: 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C and 70 deg.C; typical but non-limiting preferred embodiments of the above reaction times are: 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min and 50 min.
In the above preferred embodiment, the reaction conditions of the application satisfy at least one of the following:
the reaction pH value is 3-5, the reaction temperature is 15-50 ℃, and the reaction time is 20-40 min.
In a preferred embodiment of the present invention, the processing method of the application comprises the steps of:
(a) adding elementary iron, ferrous ions and persulfate into the organic pollutant-containing wastewater to be treated, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 0.5-20: 0.1-10: 50-100 parts;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 2-6, and then reacting at the temperature of 15-70 ℃ for 10-50min to complete the treatment;
preferably, the processing method of the application comprises the following steps:
(a) adding simple substance iron, ferrous ions and persulfate into the wastewater containing organic pollutants to be treated, and adjusting the molar ratio of the simple substance iron to the ferrous ions to the persulfate to be 1-5: 0.1-1: 50-70;
(b) and (c) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 3-5, and then reacting at the temperature of 15-50 ℃ for 20-40 min to complete the treatment.
Preferably, when ferrous sulfate is used as an iron source, the pH is adjusted to be low by using a dilute sulfuric acid solution; ferrous chloride is used as an iron source, and the pH value is adjusted to be low by using a dilute hydrochloric acid solution.
In a preferred embodiment of the present invention, the reaction method of the step (b) reaction comprises one or more of standing, stirring, shaking and ultrasound.
As a preferred embodiment, the reaction method comprises one or more of standing, stirring, shaking and ultrasound, so that the reaction can be accelerated to obtain a better treatment effect.
In the above preferred embodiment, when the reaction is oscillation, the speed of the oscillation is 200 to 250rpm, preferably 210 rpm;
typical but non-limiting preferred embodiments of the rate of the above-mentioned oscillations are: 200rpm, 210rpm, 220rpm, 230rpm, 240rpm and 250 rpm.
In the above preferred embodiment, when the reaction is ultrasound, the power of the ultrasound is 30 to 60W, preferably 40W.
The technical solution of the present invention will be further described with reference to examples and comparative examples. Note: the adding state of the simple substance iron, the ferrous ion and the persulfate in the system can be solid, solution, partial solid or partial solution as long as the corresponding molar ratio is achieved. Meanwhile, in the research, methyl red is firstly used as a model compound to explore and optimize reaction conditions, so that the optimized conditions are multiplied and fine-tuned, and the method is applied to treatment of actual printing and dyeing wastewater.
Example 1
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous sulfate heptahydrate.
2) Selection of persulfate:
the persulfate salt selected in this example was sodium persulfate.
3) Selection of elementary iron: fe powder with a particle size of 0.5-1000 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into a methyl red solution with the concentration of 200mg/L, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 0.5: 0.1: 50, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 2, and then carrying out shaking table oscillation reaction at 200rpm for 10min at the temperature of 15 ℃ to finish the treatment.
And 3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, equal volume of 1mol/L sodium hydroxide is added, the solution is centrifuged, supernatant liquid is obtained, an ultraviolet characterization is used for detecting the absorbance value of methyl red at 513nm, and the degradation rate is calculated to be 31%. The COD removal rate was 18%.
Example 2
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous sulfate heptahydrate.
2) Selection of persulfate:
the persulfate salt selected in this example was sodium persulfate.
3) Selection of elementary iron: fe powder with a particle size of 0.5-1000 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into a methyl red solution with the concentration of 200mg/L, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 20: 10: 100, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 6, and then carrying out shaking reaction on a shaker at 200rpm for 50min at the temperature of 50 ℃ to finish the treatment.
And 3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, equal volume of 1mol/L sodium hydroxide is added, the solution is centrifuged, supernatant liquid is taken, an ultraviolet characterization is used for detecting the absorbance value of methyl red at 513nm, and the degradation rate is calculated to be 93%. The COD removal rate was 76%.
Example 3
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous sulfate heptahydrate.
2) Selection of persulfate:
the persulfate salt selected in this example was sodium persulfate.
3) Selection of elementary iron: fe powder with particle size of 150-500 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into a methyl red solution with the concentration of 200mg/L, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 1: 5: 60, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 4, and then carrying out shaking table oscillation reaction at 200rpm for 20min at the temperature of 25 ℃ to finish the treatment.
And 3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, equal volume of 1mol/L sodium hydroxide is added, the solution is centrifuged, supernatant liquid is taken, an ultraviolet characterization is used for detecting the absorbance value of methyl red at 513nm, and the degradation rate is calculated to be 95%. The COD removal rate was 90%.
Example 4
1) Selection of ferrous ions:
in this embodiment, the ferrous iron source selected by the ferrous ions is ferrous acetate and ferrous sulfate heptahydrate, and the mass ratio of the ferrous iron source to the ferrous iron source is 1: 1.
2) selection of persulfate:
the persulfate salt selected in this example was sodium persulfate.
3) Selection of elementary iron: fe powder with particle size of 150-500 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into a methyl red solution with the concentration of 200mg/L, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 1: 5: 60, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 5, and then carrying out shaking table oscillation reaction at 200rpm for 20min at the temperature of 25 ℃ to finish the treatment.
And 3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, equal volume of 1mol/L sodium hydroxide is added, the supernatant is obtained by centrifugation, the absorbance value of the methyl red at 513nm is detected by ultraviolet characterization, and the degradation rate is calculated to be 95%. The COD removal rate was 90%.
From examples 3 and 4, it is clear that the selection of different ferrous iron sources has little influence on the experimental results.
Example 5
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous chloride tetrahydrate.
2) Selection of persulfate:
the persulfate selected in the embodiment is potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1: 1.
3) Selection of elementary iron: fe powder with particle size of 150-500 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into a methyl red solution with the concentration of 200mg/L, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 1: 5: 60, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 5, and then carrying out shaking table oscillation reaction at 200rpm for 20min at the temperature of 25 ℃ to finish the treatment.
And 3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, 1mol/L of sodium hydroxide with the same volume is added, the solution is centrifuged, supernatant liquid is obtained, the absorbance value of methyl red under 513nm is detected by ultraviolet characterization, and the degradation rate is calculated to be 95%. The COD removal rate was 90%.
Example 6
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous sulfate heptahydrate.
2) Selection of persulfate:
the persulfate salt selected in this example was ammonium persulfate.
3) Selection of elementary iron: fe powder with particle size of 150-500 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the mixture, wherein the COD value is between 1000 and 2000, and the absorbance A is respectively as follows: a. the436＝0.523，A525＝0.453，A620Adjusting the molar ratio of the elementary substance iron to the ferrous ions to the persulfate to 5:0.5:80 and adjusting the total volume to 50ml in the printing and dyeing wastewater of 0.638;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 4, and then carrying out shaking table oscillation reaction at 200rpm for 20min at the temperature of 25 ℃ to finish the treatment.
3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, and equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 90% after centrifugation.
Example 7
1) Selection of ferrous ions:
the ferrous iron source of choice for the ferrous ion in this example was ferrous sulfate heptahydrate.
2) Selection of persulfate:
the persulfate salt selected in this example was sodium persulfate.
3) Selection of elementary iron: fe powder with particle size of 150-500 μm.
4) The specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the mixture, wherein the COD value is between 1000 and 2000, and the absorbance A is respectively as follows: a. the436＝0.523，A525＝0.453，A620Adjusting the molar ratio of the elementary substance iron to the ferrous ions to the persulfate to 5:0.5:80 and adjusting the total volume to 50ml in the printing and dyeing wastewater of 0.638;
(b) and (c) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 4, and then performing 40W ultrasonic treatment for 15min at the temperature of 20 ℃ to perform reaction degradation, thereby finishing the treatment.
3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, and equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 90% after centrifugation.
Comparative example 1
The selection of the simple substance iron, the ferrous ions and the persulfate in the comparative example is the same as that in example 6;
4) the specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the printing and dyeing wastewater same as that in the embodiment 6, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to 1:10:7, wherein the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 1, and then carrying out shaking table oscillation reaction at 200rpm for 180min at the temperature of 25 ℃ to finish the treatment.
3ml of the solution after the reaction degradation is put into a 10ml centrifuge tube, and the equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is taken by centrifugation and is 64 percent.
Comparative example 2
The selection of the simple substance iron, the ferrous ions and the persulfate in the comparative example is the same as that in example 6;
4) the specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the printing and dyeing wastewater same as that in the embodiment 6, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to 1:10:7, wherein the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 10, and then carrying out shaking table oscillation reaction at 200rpm for 180min at the temperature of 25 ℃ to finish the treatment.
3ml of the solution after reaction and degradation is put into a 10ml centrifuge tube, and equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 57% after centrifugation.
Comparative example 3
The selection of the simple substance iron, the ferrous ions and the persulfate in the comparative example is the same as that in example 6;
4) the specific degradation process is implemented according to the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the printing and dyeing wastewater same as that in example 6, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 0.5: 3: 10, the total volume is 50 ml;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 4, and then carrying out shaking table oscillation reaction at 200rpm for 180min at the temperature of 25 ℃ to finish the treatment.
3ml of the solution after the reaction degradation is put into a 10ml centrifuge tube, and the equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 69 percent after centrifugation.
Comparative example 4
The selection of the simple substance iron, the ferrous ions and the persulfate in the comparative example is the same as that in example 6;
in the step (a) of the degradation removal process of the comparative example, the molar ratio of the elemental iron to the ferrous ions to the persulfate is 10: 1: in addition to 50, the same procedure as in example 6 was repeated.
3ml of the solution after the reaction degradation is put into a 10ml centrifuge tube, and the equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 45 percent after centrifugation.
Comparative example 5
The selection of the simple substance iron, the ferrous ions and the persulfate in the comparative example is the same as that in example 6;
this comparative example is the same as example 6 except that in the degradation step (a), the temperature is 50 ℃ and the reaction time is 10 min.
3ml of the solution after the reaction degradation is put into a 10ml centrifuge tube, and the equal volume of 1mol/L sodium hydroxide is added, and the supernatant liquid COD removal rate is 63 percent after centrifugation.
In conclusion, in the method for oxidizing organic wastewater provided by the invention, the elemental iron, the ferrous ions and the persulfate are adjusted by a specific molar ratio, so that the problem of overlarge initial ferrous ion concentration is effectively avoided; meanwhile, the long-acting stable existence of ferrous ions as an activator in a reaction system is kept, and the relative stability of the concentration of sulfate radicals is maintained. In addition, it can be seen from the above examples and comparative examples that only if each parameter is controlled within the scope of the present invention, the ideal degradation effect can be achieved, not only the degradation effect on organic pollutants is excellent, but also the degradation effect on total nitrogen is very excellent, and it can be seen that if a certain parameter is not controlled within the scope of the present invention, the ideal degradation effect, especially pH, cannot be achieved even if the degradation reaction time is prolonged, and the parameters such as the amount of each substance in the system need to be matched with each other and all formulated within the excellent range, and if the pH is controlled within the scope of the present invention, the amount of each substance is in any proportion, although there is a degradation effect, the degradation rate is not high.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The organic wastewater oxidation treatment method is characterized by comprising the steps of adding elemental iron, ferrous ions and persulfate into organic wastewater for treatment;
in the treatment method, the molar ratio of the simple substance iron to the ferrous ions to the persulfate is 0.5-20: 0.1-10: 50 to 100.
2. The organic wastewater oxidation treatment method according to claim 1, wherein in the treatment method, the molar ratio of elemental iron to ferrous ions to persulfate is 0.5-20: 0.1-10: 50-100 parts;
preferably, the molar ratio of the elementary substance iron to the ferrous ions to the persulfate is 1-10: 0.2-5: 50-85;
more preferably, the molar ratio of the elementary iron to the ferrous ions to the persulfate is 1-5: 0.1-1: 50-70.
3. The method for oxidation treatment of organic wastewater according to claim 1 or 2, wherein the elemental iron is iron powder;
preferably, the particle size of the iron powder is 0.5-1000 μm, and preferably 150-500 μm.
4. The organic wastewater oxidation treatment method according to claim 1 or 2, wherein the ferrous iron source of ferrous ions comprises at least one of ferrous sulfate heptahydrate, ferrous acetate, and ferrous chloride tetrahydrate;
preferably, the ferrous iron source of ferrous ions comprises ferrous sulfate heptahydrate.
5. The oxidation treatment method for organic wastewater according to claim 1 or 2, wherein the persulfate includes at least one of sodium persulfate, potassium persulfate, and ammonium persulfate;
preferably, the persulfate salt comprises sodium persulfate and/or potassium persulfate.
6. Use of the method for the oxidative treatment of organic wastewater according to any one of claims 1 to 5 for the treatment of wastewater containing organic pollutants;
preferably, the organic pollutant-containing wastewater is printing and dyeing wastewater with a COD value of between 1000 and 2000.
7. The use according to claim 6, wherein the reaction conditions of the use at least satisfy at least one of the following:
the reaction pH value is 2-6, the reaction temperature is 15-70 ℃, and the reaction time is 10-50 min;
preferably, the reaction conditions of the application at least satisfy at least one of the following:
the reaction pH value is 3-5, the reaction temperature is 15-50 ℃, and the reaction time is 20-40 min.
8. The application according to claim 6, characterized in that the processing method of the application comprises the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the organic pollutant-containing wastewater to be treated, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 0.5-20: 0.1-10: 50-100 parts;
(b) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 2-6, and then reacting at the temperature of 15-70 ℃ for 10-50min to complete the treatment;
preferably, the processing method of the application comprises the following steps:
(a) adding elementary iron, ferrous ions and persulfate into the wastewater containing organic pollutants to be treated, and adjusting the molar ratio of the elementary iron to the ferrous ions to the persulfate to be 1-10: 0.2-5: 60-85;
(b) and (c) adjusting the pH value of the wastewater to be treated after the molar ratio is adjusted in the step (a) to 3-5, and then reacting at the temperature of 15-50 ℃ for 20-40 min to complete the treatment.
9. The use of claim 8, wherein the reaction method of the reaction of step (b) comprises one or more of standing, stirring, shaking and ultrasound.
10. Use according to claim 9, wherein, when the reaction is an oscillation, the rate of oscillation is 200 to 250rpm, preferably 210 rpm;
preferably, when the reaction is ultrasonic, the power of the ultrasonic is 30-60W, and preferably 40W.
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Application publication date: 20200918 |