CN103663666A - Method for carrying out cooperative oxidation treatment on organic wastewater by potassium permanganate and potassium hydrogen persulfate - Google Patents
Method for carrying out cooperative oxidation treatment on organic wastewater by potassium permanganate and potassium hydrogen persulfate Download PDFInfo
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Abstract
The invention provides a method for carrying out cooperative oxidation treatment on organic wastewater by potassium permanganate and potassium hydrogen persulfate. According to the treatment method, the treatment efficiency of the wastewater is improved and the dosage of an oxidant is reduced. The method comprises the following steps: (1) selecting the organic wastewater with the pH (Potential of Hydrogen) which is less than or equal to 10 or adjusting the pH of the organic wastewater to be less than or equal to 10, wherein organic matters in the organic wastewater contain unsaturated bonds; and (2) adding the potassium permanganate and the potassium hydrogen persulfate into the organic wastewater to be treated at the same time; or within half an hour after adding the potassium permanganate into the organic wastewater, adding the potassium hydrogen persulfate and agitating to react for 1-4 hours. According to the method, a catalyst does not need to be added in the reaction process and a byproduct obtained by the reaction of the potassium permanganate can be used as a catalyst for stimulating the oxidization performance of hydrogen persulfate; the dosage of medicaments is saved, the cost is saved and an operation process is simplified. The method provided by the invention is simple in process operation and good in pollution cleaning effects and has good treatment effects on various types of organic wastewater, particularly phenols and anilines wastewater.
Description
Technical field
The invention belongs to environmental technology field, relate to a kind of method that potassium permanganate and potassium hydrogen persulfate synergistic oxidation are processed organic waste water.
Background technology
Developing rapidly of national economy, the discharge of " three wastes " material of the generation in productive life process, has caused serious soil and groundwater to pollute, and water and soil pollutes HUMAN HEALTH, socio-economic development and ecotope is constituted a serious threat.Water pollution control is one of hot issue of paying close attention to of current social, and the organic pollution materials of chemical oxidation technology in can sewage oxidation treatment, is one of main treatment technology of organic waste water.The oxygenant of chemical oxidation utilization mainly contains chlorine, dioxide peroxide, ozone, Fenton reagent and potassium permanganate etc., with respect to other several oxygenants, potassium permanganate is solid, have the transportation of convenience and storage, cheap, the feature such as be easy to obtain, and its oxidation efficiency affected by ionic strength and pH value less, better to gas chromatography oxidation effectivenesses such as the phenols containing unsaturated link(age) and phenyl aminess.But use potassium permanganate oxidation organism also to have some limitations, first, the oxidation effectiveness of potassium permanganate is limited, and a lot of organism are difficult to exhaustive oxidation, and the chemical oxygen demand (COD) of waste water (COD) or total organic carbon (TOC) are removed to scarce capacity; When the large usage quantity of potassium permanganate, the Manganse Dioxide producing is (under weakly alkaline, neutrality, solutions of weak acidity, product is Manganse Dioxide, and only under strong acidic condition, (for example pH≤3) produce mn ion) can cause the perception of waste water poor, increase follow-up processing cost.
Potassium hydrogen persulfate (KHSO
5) be a kind of novel oxygenant, by adding transition metal exciting agent (such as iron ion, mn ion, manganese oxide, cobalt ion etc.), can produce the extremely strong sulfate radical free radical (SO of oxidation capacity
4 2-), this oxygenant has very strong oxidation capacity by sulfate radical, can exhaustive oxidation phenol, miscellaneous organism such as aniline, naphthols, and reaction product is sulfate radical, carbonic acid gas, water and other inorganicss.Potassium hydrogen persulfate is the same with potassium permanganate, and it is little that oxidation capacity is affected by pH value, and only produces sulfate radical after reaction, without secondary retained, can be used for the processing of multiple organic waste water.
Potassium permanganate oxidation and potassium hydrogen persulfate method for oxidation are all that a kind of of existing wastewater oxidation treatment process effectively supplemented, but when these two kinds of methods are applied to treatment of Organic Wastewater separately, all have certain deficiency.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of utilizing potassium permanganate and potassium hydrogen persulfate synergistic oxidation to process organic waste water.This treatment process improves the processing efficiency of waste water, reduces the consumption of oxygenant.
The principle of oxidation treatment method of the present invention is: in waste water, contain the organic pollutant (Org.) of unsaturated link(age) by potassium permanganate oxidation, self be reduced to the manganese oxide hydrate (MnxO of nascent state
yh
2o), the manganese oxide hydrate of nascent state can effectively excite potassium hydrogen persulfate, produces persulphate free radical, further in oxidized waste water by the organic pollutant of potassium permanganate partial oxidation (Org.Intermediates), thereby accelerate Pollutants in Wastewater
The removal of degraded and waste water total organic carbon, as follows.
The present invention realizes by following technical scheme:
1) select pH≤10 organic waste water, or organic waste water is adjusted to pH≤10, and in described organic waste water, organism contains unsaturated link(age);
2) potassium permanganate and potassium hydrogen persulfate are joined in pending organic waste water simultaneously, or potassium permanganate was added after organic waste water in half an hour, add potassium hydrogen persulfate, stir, react 1～4 hour.
For improving the utilization ratio of two kinds of oxygenants, the consumption of potassium permanganate is generally the mineralising equivalent of 0.5～1 times of organic waste water; And the consumption of potassium hydrogen persulfate is generally the mineralising equivalent of 1 times of organic waste water.
Wherein, the administration form of potassium hydrogen persulfate is potassium hydrogen persulfate composite salt, and commodity are called Oxone, the composite salt being formed by potassium hydrogen persulfate, sal enixum and potassium sulfate, and its oxidation effective ingredient is potassium hydrogen persulfate.
Measure the concentration of Pollutants in Wastewater, or the total organic carbon of waste water, can evaluate degraded and the mineralization degree of the organic pollutant in waste water.
Below further discuss the technical characterictic that utilizes potassium permanganate and potassium hydrogen persulfate synergistic oxidation to process organic waste water.
One of technical essential of the inventive method is the mode that adds of potassium permanganate and potassium hydrogen persulfate.The oxidation susceptibility of potassium hydrogen persulfate accesses the manganese oxide hydrate that the key fully exciting is nascent state.Therefore, potassium permanganate and potassium hydrogen persulfate need to be joined in waste water simultaneously, or join (in half an hour) in waste water early than potassium hydrogen persulfate.The nascent state manganese oxide hydrate producing after potassium permanganate partial oxidation is nanometer, amorphousness, can excite persulfuric acid hydrogen salt, produces sulfate radical free radical, exhaustive oxidation organism.For guaranteeing fully contacting of nascent state manganese oxide hydrate and persulfuric acid hydrogen salt, whole process should stir fully.Experiment shows, along with time lengthening, nascent state manganese oxide hydrate can change the cotton-shaped black Manganse Dioxide of large particle diameter gradually into, once and form stable Manganse Dioxide (general half hour), then add potassium hydrogen persulfate, may not observe synergistic oxidation effect.
Two of the technical essential of the inventive method is the add-on of potassium permanganate and persulphate.For improving the utilization ratio of two kinds of oxygenants, save oxygenant consumption and cost for wastewater treatment, the consumption of potassium permanganate is generally the mineralising equivalent of 0.5～1 times of waste water; And the consumption of potassium hydrogen persulfate is generally the mineralising equivalent of 1 times of waste water.Mineralising is defined as the elements such as carbon in the organic pollutant in waste water, hydrogen, oxygen, nitrogen and all transfers the inorganicss such as carbonic acid gas, water, nitrogen to.The oxygenant of 1 times of mineralising equivalent, this oxygenant becomes stable reduction valence state completely, and its total electronic number obtaining equates completely with the electronic number that mineralization of organic material in waste water (being converted into the inorganicss such as carbonic acid gas, water) loses.Take the organic pollutant of phenol in waste water, as follows to illustrating of mineralising equivalent:
C
6h
6o+6O
2→ 6CO
2+ 3H
2o(1 moles of phenol mineralising, loses 24 moles of electronics)
Therefore potassium permanganate is processed 1 moles of phenol, 1 times of mineralising equivalent be 8 moles; Potassium hydrogen persulfate is processed 1 moles of phenol, and 1 times of mineralising equivalent is 12 moles.
Three of the technical essential of the inventive method is the selection of organic waste water.Organic waste water can be for containing the organism of single kind, or gas chromatography, but wherein have at least a kind of organism by potassium permanganate oxidation, to produce nascent state hydrated manganese dioxide.In general, under weakly alkaline, neutrality and acidic conditions, the organism that contains unsaturated link(age) greatly can both be by potassium permanganate oxidation, for example phenol, aniline, naphthols and substituting group derivative thereof, chloro organic solvent quasi-molecule trieline, zellon and some azo-compounds, nitrogen heterocyclic etc.In waste water, contain these and can, by the organism of potassium permanganate partial oxidation, just can realize the object that potassium permanganate and potassium hydrogen persulfate synergistic oxidation are processed waste water.
Four of the technical essential of the inventive method is that organic waste water can not be alkaline (pH > 10).Under strong alkaline condition, nascent state manganese oxide hydrate cannot generate.Meanwhile, strong alkaline condition also can cause the alkalescence of potassium hydrogen persulfate to decompose, and is unfavorable for being oxidized the performance of usefulness.
The inventive method is combined use by potassium permanganate and potassium hydrogen persulfate, reduced the consumption of potassium permanganate, and potassium hydrogen persulfate does not need extra exciting agent yet, just can bring into play sulfate radical free-radical oxidn effect, thorough decomposing organic matter, and realize the synergistic effect that oxygenant uses (effect of combining use be greater than that the two uses separately adding and).
The present invention compares with existing wastewater oxidation treatment process, has following outstanding superiority:
(1) oxygenant that the present invention uses is potassium permanganate and persulfuric acid hydrogen salt, is all the New Solid oxygenant of green safety, and stable chemical nature, easily stores and transport.
(2) in reaction process of the present invention, need not add in addition catalyzer, the reacted by product of potassium permanganate can be used as the oxidation susceptibility that catalyzer excites persulfuric acid hydrogen salt, saves dosing, cost-saving, simplifies the operation course.
(3) compare with independent use potassium permanganate or hydrogen persulfate salt, combine and use to produce synergistic effect, the efficiency that oxide treatment efficiency is better than single use potassium permanganate, potassium hydrogen persulfate add and, and reacted product safety non-pollution.
(4) technological operation of the present invention is simple, and scrubbing is effective, splendid to the treatment effect of multiple organic waste water, particularly phenols, amino benzene analog waste water.
(5) the present invention relies on not strong to the pH of waste water.Except strong basicity waste water, do not need organic waste water to carry out pH regulator.With respect to Fenton reagent oxidising process, reduced acid adjustment, adjusted the link of alkali.
Accompanying drawing explanation
Fig. 1 potassium permanganate and potassium hydrogen persulfate associated treatment organic pollutant with process respectively organic TOC removal effect comparison diagram (aniline, phenol, naphthols result are the result in embodiment).
Embodiment
By the following examples and comparative example, can have better understanding to the present invention, but these embodiment can not be interpreted as limiting the scope of the invention.
Embodiment 1
In this example, aniline organic waste water is pending object, and concentration of aniline is 100mg/l, and corresponding total content of organic carbon is 26.79mg/L, and wastewater pH regulates.Potassium permanganate and persulfuric acid hydrogen salt are solution, KMnO
4strength of solution is that 0.25mol/l potassium hydrogen persulfate double salt (Oxone) concentration of aqueous solution is 198.38g/l.Experiment is divided into four groups, and all adopting the Erlenmeyer flask with glass stopper is reaction vessel.Experimental group 0 is blank, does not add oxygenant.Experimental group 1 is to use separately potassium permanganate, to the potassium permanganate solution 1.3ml that adds 0.25mol/l in 100mL waste water, reaction 4h; Second group is used separately potassium hydrogen persulfate double salt, to the potassium hydrogen persulfate complex salt solution 1ml that adds 198.38g/l in 100mL waste water, and reaction 4h; Test associating potassium permanganate and persulfuric acid hydrogen salt for the 3rd group, in 100mL waste water, first add the potassium permanganate solution 1.3ml of 0.25mol/l, after shaking bed reaction 10min, add again the hydrogen persulfate salts solution 1ml of 198.38g/l, continue to react to 4h.After having reacted, measure the organic carbon content of solution by total organic carbon analyzer, evaluate organic carbon clearance, result is as shown in table 1.As can be seen from the table, the efficiency that potassium permanganate is oxidized separately aniline is 36.10%, the independent Use Limitation rate of potassium hydrogen persulfate is 9.18%, and adding and being 45.28% of the two is lower 10 percentage points than the processing efficiency 54.95% of potassium permanganate and potassium hydrogen persulfate synergistic oxidation.
Table 1 potassium permanganate, potassium hydrogen persulfate and the two are combined the total organic Carbon removal using aniline waste water
Embodiment 2
In this example, phenol organic waste water is pending object, and phenol concentration is 100mg/l, and corresponding total content of organic carbon is 40.84mg/L, and waste water is subacidity (pH is 6).Potassium permanganate and persulfuric acid hydrogen salt are solution, KMnO
4strength of solution is that 0.25mol/l potassium hydrogen persulfate double salt (Oxone) concentration of aqueous solution is 198.38g/l.Experiment is divided into four groups, and all adopting the Erlenmeyer flask with glass stopper is reaction vessel.Experimental group 0 is blank, does not add oxygenant.Experimental group 1 is to use separately potassium permanganate, to the potassium permanganate solution 2ml that adds 0.25mol/l in 100mL waste water, reaction 4h; Second group is used separately potassium hydrogen persulfate double salt, to the potassium hydrogen persulfate complex salt solution 1.55ml that adds 198.38g/l in 100mL waste water, and reaction 4h; Test associating potassium permanganate and persulfuric acid hydrogen salt for the 3rd group, in 100mL waste water, first add the potassium permanganate solution 2ml of 0.25mol/l, after shaking bed reaction 10min, add again the potassium hydrogen persulfate complex salt solution 1.55ml of 198.38g/l, continue to react to 4h.After having reacted, measure the organic carbon content of solution by total organic carbon analyzer, evaluate organic carbon clearance, result is as shown in table 1.As can be seen from the table, the efficiency that potassium permanganate is oxidized separately aniline is 35.77%, the independent Use Limitation rate of potassium hydrogen persulfate is 4.06%, and adding and being 39.83% of the two is lower 30 percentage points than the processing efficiency 69.81% of potassium permanganate and potassium hydrogen persulfate synergistic oxidation.
Table 2 potassium permanganate, potassium hydrogen persulfate and the two are combined the total organic Carbon removal that uses Pyrogentisinic Acid's waste water
Embodiment 3
In this example, 2-Naphthol organic waste water is pending object, and naphthols concentration is 100mg/l, and corresponding total content of organic carbon is 137.7mg/L, and wastewater pH is 8.Potassium permanganate and persulfuric acid hydrogen salt are solution, KMnO
4strength of solution is that 0.25mol/l potassium hydrogen persulfate double salt (Oxone) concentration of aqueous solution is 198.38g/l.Experiment is divided into four groups, and all adopting the Erlenmeyer flask with glass stopper is reaction vessel.Experimental group 0 is blank, does not add oxygenant.Experimental group 1 is to use separately potassium permanganate, to the potassium permanganate solution 2ml that adds 0.25mol/l in 100mL waste water, reaction 4h; Second group is used separately potassium hydrogen persulfate double salt, to the potassium hydrogen persulfate complex salt solution 1.55ml that adds 198.38g/l in 100mL waste water, and reaction 4h; Test associating potassium permanganate and persulfuric acid hydrogen salt (simultaneously adding) for the 3rd group, in 100mL waste water, add the potassium permanganate solution 3.2ml of 0.25mol/l and the potassium hydrogen persulfate complex salt solution of 2.5ml simultaneously, shaking bed reaction 4h.After having reacted, measure the organic carbon content of solution by total organic carbon analyzer, evaluate organic carbon clearance, result is as shown in table 1.
Table 3 potassium permanganate, potassium hydrogen persulfate and the two are combined the total organic Carbon removal using naphthols waste water
As can be seen from the table, the efficiency that potassium permanganate is oxidized separately aniline is 59.75%, the independent Use Limitation rate of potassium hydrogen persulfate is 0, and adding and being 59.83% of the two is lower 18.36 percentage points than the processing efficiency 78.11% of potassium permanganate and potassium hydrogen persulfate synergistic oxidation.
Claims (4)
1. potassium permanganate and potassium hydrogen persulfate synergistic oxidation are processed a method for organic waste water, it is characterized in that, comprise the steps:
Select pH≤10 organic waste water, or organic waste water is adjusted to pH≤10, and in described organic waste water, organism contains unsaturated link(age);
Potassium permanganate and potassium hydrogen persulfate are joined in pending organic waste water simultaneously, or potassium permanganate was added after organic waste water in half an hour, add potassium hydrogen persulfate, stir, react 1 ~ 4 hour.
2. method according to claim 1, is characterized in that, the consumption of described potassium permanganate is the mineralising equivalent of 0.5 ~ 1 times of organic waste water; The consumption of described potassium hydrogen persulfate is the mineralising equivalent of 1 times of organic waste water.
3. method according to claim 1, is characterized in that, the administration form of described potassium hydrogen persulfate is potassium hydrogen persulfate composite salt, potassium hydrogen persulfate, sal enixum and potassium sulfate, consists of.
4. method according to claim 1, is characterized in that, comprises the organism that phenol, aniline, naphthols or their substitutive derivatives etc. contain unsaturated link(age) in described organic waste water.
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Application publication date: 20140326 |