CN111056665B

CN111056665B - Method for cooperatively treating organic matter sewage by using ionic liquid and hydrogen peroxide

Info

Publication number: CN111056665B
Application number: CN201910964264.1A
Authority: CN
Inventors: 贲永光; 周少奇
Original assignee: GUIZHOU ACADEMY OF SCIENCES; South China University of Technology SCUT; Guangdong Pharmaceutical University
Current assignee: GUIZHOU ACADEMY OF SCIENCES; South China University of Technology SCUT; Guangdong Pharmaceutical University
Priority date: 2019-10-11
Filing date: 2019-10-11
Publication date: 2022-08-26
Anticipated expiration: 2039-10-11
Also published as: CN111056665A

Abstract

The invention discloses a method for degrading organic matter sewage by ionic liquid and hydrogen peroxide, belonging to the technical field of environmental protection. On the basis, the influence of changing the added amount of the ionic liquid on the aniline degradation effect is researched, and the optimal process condition for degrading aniline by the ionic liquid in cooperation with hydrogen peroxide is determined: the concentration of the ionic liquid is 0.6g/L, the adding amount of the hydrogen peroxide is 0.3mL, the time is 10min, the pH value is 6, the initial concentration of the aniline wastewater is 30mg/L, the room temperature is about 18 ℃, and the degradation rate is 96.2%. Finally, the ionic liquid is found to have higher degradation rate in cooperation with the hydrogen peroxide, and the treated aniline sewage reaches the national first-grade discharge standard.

Description

Method for treating organic matter sewage by using ionic liquid-hydrogen peroxide in synergy mode

Technical Field

The invention relates to the technical field of environmental protection, in particular to a method for treating organic matter sewage by using ionic liquid and hydrogen peroxide in a synergistic manner.

Background

With the rapid development of industry, the number of sewage types is rapidly increased, and the pollution to water bodies is also becoming serious. The organic sewage is more complicated in composition and type and more difficult to treat.

For example, municipal sludge anaerobic ammonia oxidation effluent and landfill leachate are high-concentration, high-pollution and degradation-resistant organic sewage. The water contains aerobic organic pollutants and various metals and ammonia nitrogen compounds, and the concentration of COD and BOD in the water is as high as tens of thousands and is far higher than that of urban sewage.

In addition, non-chlorinated aromatic compounds such as naphthalene and phenanthrene, chlorinated aromatic compounds, phosphate esters, phthalate esters, phenolic compounds, aniline compounds, and the like, which are difficult to biodegrade, are contained in such sewage. The quality of the sewage becomes worse with the lapse of time, and the BOD/COD is less than 0.1, and the sewage has almost no biodegradability.

The current treatment methods for such wastewater include: adsorption, chemical precipitation, density separation, catalytic oxidation, reverse osmosis, gas stripping, and wet oxidation. The efficiency of degrading organic matters by a biochemical method can reach 50-80%, but the cost is higher, and the method is not suitable for treating a large amount of sewage.

Disclosure of Invention

The invention aims to provide a method for treating organic sewage by using ionic liquid-hydrogen peroxide in a synergistic manner, so that the degradation rate of organic matters is improved.

In order to achieve the purpose, the invention provides the following scheme:

the invention provides a method for treating organic sewage by using ionic liquid-hydrogen peroxide in a synergistic manner, which comprises the following steps of:

(1) adjusting the pH value of the organic matter sewage to 6-7, adding hydrogen peroxide and ionic liquid into the organic matter sewage, and standing for 10-60 min; taking aniline simulated organic sewage as an example, the degradation rate of aniline gradually increases with the time, and reaches 79.2% at 40 min. And the reaction time is increased, the degradation rate of the aniline is not obviously increased, and the degradation rate tends to be stable, which indicates that the oxidation reaction is close to an equilibrium state, and the reaction time is continuously prolonged without influence on the equilibrium state. According to the theory of free radical reaction, hydrogen peroxide is decomposed to generate OH free radicals and H free radicals, and when the time is prolonged properly, a large amount of very active OH free radicals thoroughly oxidize organic matters in water into CO ₂ And H ₂ And (O). Along with the prolonging of time, free radicals or charged ions in water are gradually reduced, so that the degradation rate is gradually reduced until the degradation rate is stopped;

(2) adding a potassium hydrogen sulfate solution into the reaction liquid obtained in the step (1) to adjust the pH value to 1.5-2.0, adding 1 drop of a sodium nitrite solution, shaking up, and standing for 3-5 min;

(3) and (3) adding an ammonium sulfamate solution into the reaction solution obtained in the step (2), fully oscillating, and standing for 3-5 min.

Preferably, the addition amount of the hydrogen peroxide in the organic sewage is 1 to 6 percent. Taking aniline simulated organic matter sewage as an example, the degradation rate of aniline in sewage is increased and then obviously reduced along with the increase of the adding amount of hydrogen peroxide. When the addition amount of hydrogen peroxide is 3%, the degradation rate of aniline reaches a maximum of 86.8%. The adding amount of the hydrogen peroxide has a crucial influence on the sewage treatment effect: at lower hydrogen peroxide concentrations, the amount of OH increases with increasing hydrogen peroxide dosage, thus increasing the degradation rate; however, when the amount of hydrogen peroxide added reaches a certain level, the degradation rate of aniline decreases because when the amount of hydrogen peroxide added is too high, the excess hydrogen peroxide cannot generate more OH radicals by decomposition, and the following reaction occurs:

H ₂ O ₂ +·OH→HOO·+H ₂ O

in addition, the following reactions occur between radicals:

HOO·+·OH→H ₂ O+O ₂

2·OH→H ₂ O ₂

these reactions not only eliminate the OH radicals initially produced, but also consume hydrogen peroxide and inhibit the production of OH, but also generate a large amount of perhydroxyl radicals (HO) due to the presence of excessive hydrogen peroxide ₂ HO) although ₂ Is capable of promoting free radical chain reactions and HO ₂ It has an oxidizing capacity of its own, but its efficiency is much lower than that of the hydroxyl radical (HO.), and for some organic substrates, HO ₂ No degradation capability, and finally a reduction in the degradation rate of aniline. Therefore, the more preferable amount of hydrogen peroxide to be added to the organic wastewater is 3%.

Preferably, the concentration of the ionic liquid in the organic sewage is 0.2g/L-1.2 g/L. Taking aniline as an example of simulating organic matter sewage, the degradation rate of aniline is increased until the aniline is stable along with the increase of the concentration of ionic liquid in the sewage, and the highest degradation rate of aniline can reach 96.1 percent, which is higher than 87.1 percent of the highest degradation rate of aniline degraded by the action of hydrogen peroxide alone, so that the added ionic liquid and hydrogen peroxide have synergistic effect. The ionic liquid is added into the solution, so that the degradation rate of the organic matters can be increased.

Preferably, the ionic liquid is an alkyl-substituted imidazole ionic liquid.

Preferably, the concentration of the organic matters in the organic matter sewage is 5mg/L-35 mg/L. Taking aniline simulated organic wastewater as an example, the degradation rate of aniline in the concentration range of 5.0mg/L-30.0mg/L increases with the increase of the initial concentration of aniline simulated wastewater, i.e. the initial concentration is higher to facilitate the degradation, the initial concentration is lower to reduce the degradation rate, but the degradation rate increases more and more slowly with the increase of the aniline concentration. The aniline concentration is increased, the contact probability of aniline and active free radicals is increased under a certain condition, the attack chance of OH is increased, the reaction rate is accelerated in the same time, and the degradation rate is increased; the initial concentration of aniline continues to increase, and under the condition of a certain addition amount of hydrogen peroxide, the degradation rate is gradually increased and gradually approaches to be gentle under the influence of the amount of hydrogen peroxide. The initial concentration of the organic matter-containing wastewater is more preferably 30.0 mg/L.

Preferably, the reaction temperature is room temperature. Because the reaction process contains hydrogen peroxide, the hydrogen peroxide is decomposed due to overhigh temperature, thereby reducing the degradation rate of organic matters.

Taking organic sewage aniline sewage as an example, the invention researches the influence of hydrogen peroxide on aniline degradation in the organic sewage under different factors, and researches the influence of ionic liquid cooperating with hydrogen peroxide on aniline degradation in water on the basis to obtain the optimal process conditions for degrading aniline by hydrogen peroxide and ionic liquid cooperating with hydrogen peroxide: under the optimal conditions that the concentration of the ionic liquid is 0.6g/L, the addition amount of the hydrogen peroxide is 0.3mL, the time is 10min, the pH value is 6, the initial concentration of the aniline wastewater is 30mg/L, and the room temperature is about 18 ℃, the degradation rate of the aniline wastewater degraded by the ionic liquid and the hydrogen peroxide is 96.2%, which is far higher than the degradation rate of the aniline wastewater degraded by the hydrogen peroxide alone which is 87.1%. The ionic liquid and the hydrogen peroxide have higher degradation rate on the organic matters in the organic matter sewage, and the aniline sewage is taken as an example, so that the low-concentration aniline sewage reaches the national first-level discharge standard.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.

FIG. 1 is a standard curve for aniline;

FIG. 2 is a graph showing the effect of hydrogen peroxide alone on the degradation rate of aniline for an initial concentration of aniline degrading solution;

FIG. 3 is a graph of the effect of hydrogen peroxide alone on the degradation rate of aniline by pH of a solution of degraded aniline;

FIG. 4 is a graph showing the effect of hydrogen peroxide dosage on aniline solution degradation rate by hydrogen peroxide alone;

FIG. 5 is the effect of reaction time for degrading aniline solution by hydrogen peroxide alone on aniline degradation rate;

FIG. 6 is a graph showing the effect of ionic liquid on the degradation rate of aniline by the concentration of ionic liquid in aniline solution under the synergistic effect of ionic liquid and hydrogen peroxide.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

Preparation of main reagents in the embodiment of the invention:

aniline (C) ₆ H ₅ NH ₂ ) Standard stock solution (5.002 g/L): adding 10mL of 0.05mol/L sulfuric acid standard solution into a 25mL volumetric flask, weighing, adding 3-5 drops of aniline reagent, weighing again, diluting with 0.05mol/L sulfuric acid solution to a scale mark, and shaking up. Calculating the aniline content in each milliliter of solution, and storing the aniline as stock solution in a refrigerator (capable of being stored for two months);

aniline standard use solution (10 mg/L): diluting aniline standard stock solution with 0.05mol/L sulfuric acid solution to obtain standard solution containing 10.0 μ g per ml (prepared when used);

aniline simulated sewage (K × 10.0 mg/L): diluting aniline standard stock solution with 0.05mol/L sulfuric acid solution to obtain aniline simulated sewage (prepared when used) containing K × 10.0mg (K is 0.5,1,1.5,2,2.5,3) per liter;

0.05mol/L sulfuric acid solution: transferring 3mL of sulfuric acid, adding the sulfuric acid into water, and diluting to 1000 mL;

10% aqueous potassium hydrogen sulfate solution: weighing 10g of potassium bisulfate, dissolving in a small amount of water, and diluting to 100 mL;

5% aqueous sodium nitrite solution: weighing 5g of sodium nitrite, dissolving in a small amount of water, and diluting to 100mL (storing in a brown bottle and storing in a refrigerator);

2.5% aqueous ammonium sulfamate solution: weighing 2.5g of ammonium sulfamate, dissolving in a small amount of water, and diluting to 100mL (storing in a brown bottle and storing in a refrigerator);

2% aqueous solution of ethylenediamine hydrochloride (NEDA): 2.0g of NEDA was weighed, dissolved in a small amount of water and diluted to 100 mL. When the preparation is carried out, the components are completely dissolved when the solution is warmed on a water bath until the solution is clear, the solution is stored in a brown bottle after being filtered, and the solution is stored in a refrigerator, so that the preparation is not suitable for more preparation, and the preparation is carried out again when the solution is turbid.

It should be noted that: the temperature has a large influence on the color reaction, the optimal temperature is 22-30 ℃, and the color can be developed in a constant-temperature water bath or a method for simultaneously making a standard curve is adopted to eliminate the temperature influence.

The ionic liquid used in the examples of the present invention was [ BMIM ]]PF ₆ From Aladdin.

The chemical reagents and apparatus of the present invention are commercially available.

The concentrations of the reagents in the present invention are mass fractions unless otherwise specified.

EXAMPLE 1 preparation of Standard Curve

A25 mL volumetric flask with 7 bottles was taken, and 0.00 mL, 0.25 mL, 0.50 mL, 1.00 mL, 2.00 mL, 3.00 mL, and 4.00mL of aniline standard use solution were added, and water was added to 10mL and shaken up. Adding 0.6mL of 10% potassium bisulfate solution to adjust pH to 1.5-2.0 (measured by precision pH paper), adding 1 drop of 5% sodium nitrite solution, shaking, and standing for 3 min. 0.5mL of 2.5% ammonium sulfamate solution was added, followed by shaking thoroughly and standing for 3 min. After bubbles are removed, 1.0mL of 2% NEDA solution is added, diluted to the scale with water, shaken up and placed for 30 min.

The absorbance was measured at 545mm wavelength using a 10mm cuvette with water as reference. And (3) taking the measured absorbance minus the absorbance of the blank test as an abscissa and the corresponding aniline content as an ordinate to draw a standard curve, which is shown in figure 1.

The obtained data are subjected to regression treatment to obtain a standard curve regression equation of A-0.4952C +0.0019, R ² The results showed that the concentration C had a good linear relationship with the absorbance A in the measurement range of 0 to 1.6mg/L, which was 0.9998.

Example 2 calculation of degradation Rate

And (3) taking 30mL of aniline simulated sewage, and adding hydrogen peroxide and ionic liquid to carry out degradation reaction. 0.4mL of the reacted solution was taken out of a 25mL volumetric flask, and water was added to 10mL and shaken up. Adding 0.6mL 10% potassium bisulfate solution to adjust pH to 1.5-2.0 (measured by precision pH paper), adding 1 drop of 5% sodium nitrite solution, shaking, and standing for 3 min. 0.5mL of 2.5% ammonium sulfamate solution was added, and the mixture was shaken well and allowed to stand for 3 min. After bubbles are removed, 1.0mL of 2% NEDA solution is added, diluted to the scale with water, shaken up and placed for 30 min. Measuring the content of aniline in a water sample by using a visible spectrophotometer at the 545mm wavelength, and calculating the degradation rate according to the following formula:

wherein:

C ₁ the initial concentration (mg/L) of the aniline sewage;

C ₂ the concentration of the aniline sewage after degradation (mg/L);

V ₁ the volume (mL) of the measured aniline wastewater;

V ₂ is the volume sum (mL) of hydrogen peroxide and ionic liquid.

EXAMPLE 3 Effect of initial concentration on the degradation Rate of aniline during degradation of Aniline with Hydrogen peroxide alone

Aniline simulated sewage with initial aniline concentrations of 5.0mg/L, 10.0mg/L, 15.0mg/L, 20.0mg/L, 25.0mg/L and 30.0mg/L is prepared, wherein each 30mL of aniline simulated sewage has an initial pH value of 6.0, an added amount of hydrogen peroxide of 0.2mL, a reaction temperature of room temperature (about 18 ℃) and a reaction time of 30min, and the single hydrogen peroxide degradation effect of aniline under different initial concentrations is shown in figure 2.

As can be seen from FIG. 2, the degradation rate of aniline in the concentration range of 5.0mg/L-30.0mg/L increases with the increase of the initial concentration of aniline-simulated sewage, i.e. the higher initial concentration is favorable for the degradation of aniline-simulated sewage, but the lower initial concentration is rather low, but the degradation rate increases more and more slowly with the increase of aniline concentration. The aniline concentration is increased, the contact probability of aniline and active free radicals is increased under a certain condition, the attack chance of OH is increased, the reaction rate is accelerated in the same time, and the degradation rate is increased; the initial concentration of aniline continues to increase, and under the influence of the amount of hydrogen peroxide, the degradation rate increases more and more slowly and approaches to be flat. From the viewpoint of favoring the degradation rate, a higher initial concentration should be selected.

EXAMPLE 4 Effect of pH on the degradation Rate of aniline during the degradation of Aniline with Hydrogen peroxide alone

6 parts of aniline simulated sewage with the initial concentration of 30.0mg/L are prepared, each 30mL, the addition amount of hydrogen peroxide is 0.2mL, the reaction temperature is room temperature (about 18 ℃), the reaction time is 30min, and the influence of the pH values of the solutions of 2, 4, 6, 8, 10 and 12 on the single hydrogen peroxide degradation effect of aniline is examined, as shown in FIG. 3.

As can be seen from FIG. 3, when the solution is weakly acidic, the degradation rate is higher, indicating that aniline degradation can be promoted in a weakly acidic environment. When the pH value of the solution is 6, the degradation rate of the aniline can reach 82.7%. It is considered by analysis that hydrogen peroxide is weakly acidic, is unstable in an alkaline solution, may decompose to generate oxygen and water to lose its oxidizing ability, and further, HCO in the solution is present at a high pH ₃ ^- And CO ₃ ^2- Increase in the amount of both the active ingredients are OH scavengers, consume free radicals, decrease the degradation rate ^[28] When the pH value is too low, H in the solution ⁺ Is an OH scavenger, the following reaction occurs:

H ⁺ +·OH→H ₂ O

the generation of OH is not facilitated, and the degradation rate of aniline is also reduced; the aniline is weakly alkaline and exists in an ion form under a weakly acidic condition, is beneficial to the reaction with OH, and has higher degradation rate. Therefore, the solution should be kept weakly acidic during the experiment, which is more favorable for the degradation of aniline.

EXAMPLE 5 Effect of hydrogen peroxide dosage on aniline degradation Rate in the degradation of aniline with Hydrogen peroxide alone

6 portions of aniline-simulated wastewater each having an initial concentration of 30.0mg/L, 30mL each, a solution pH of 6.0, a reaction temperature of room temperature (about 18 ℃ C.), and a reaction time of 30min were prepared, and the effects of the amounts of hydrogen peroxide added, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, and 0.6mL, on the effect of degrading aniline by hydrogen peroxide alone were examined, as shown in FIG. 4.

The experimental result shows that the degradation rate of the aniline in the sewage is increased and then obviously reduced along with the increase of the adding amount of the hydrogen peroxide. When the amount of hydrogen peroxide added was 0.3mL, the degradation rate of aniline reached a maximum of 86.8%. The adding amount of the hydrogen peroxide has a crucial influence on the sewage treatment effect: at lower hydrogen peroxide concentrations, the amount of OH increases with increasing hydrogen peroxide dosage, thus increasing the degradation rate; however, when the amount of hydrogen peroxide added reaches a certain level, the degradation rate of aniline decreases because when the amount of hydrogen peroxide added is too high, the excess hydrogen peroxide cannot generate more OH radicals by decomposition, and the following reaction occurs:

H ₂ O ₂ +·OH→HOO·+H ₂ O

in addition, the following reactions between radicals occur:

HOO·+·OH→H ₂ O+O ₂

2·OH→H ₂ O ₂

these reactions not only eliminate the initially generated OH radicals and consume hydrogen peroxide while suppressing the generation of OH, but also generate a large amount of perhydroxyl radicals (HO) due to the presence of excessive hydrogen peroxide ₂ HO), although ₂ Is capable of promoting free radical chain reactions and HO ₂ Intrinsic oxidizing power, but far less efficient than the hydroxyl radical (HO. cndot.)) And for some organic substrates, HO ₂ No degradation capability, and finally a reduction in the degradation rate of aniline.

EXAMPLE 6 Effect of reaction time on degradation Rate of Aniline during Hydrogen peroxide alone degradation of Aniline

6 parts of aniline simulated sewage with the initial concentration of 30.0mg/L, each 30mL, the pH value of the solution of 6.0, the reaction temperature of room temperature (about 18 ℃), and the addition amount of hydrogen peroxide of 0.2mL are prepared, and the influence of the reaction time of 10min, 20min, 30min, 40min, 50min and 60min on the single hydrogen peroxide degradation effect of aniline is examined, as shown in FIG. 5.

From the aniline degradation results (fig. 5), it can be seen that the degradation rate of aniline increases gradually with time, reaching 79.2% at 40 min. And the reaction time is increased, the degradation rate of the aniline is not obviously increased, and the degradation rate tends to be stable, which shows that the oxidation reaction is close to the equilibrium state, and the reaction time is continuously prolonged without influence on the equilibrium state. According to the theory of free radical reaction, hydrogen peroxide is decomposed to generate OH free radicals and H free radicals, and when the time is prolonged properly, a large amount of very active OH free radicals thoroughly oxidize organic matters in water into CO ₂ And H ₂ And O. With the time, free radicals or charged ions in water gradually decrease, so that the degradation rate gradually slows down until the degradation rate stops.

Results and analysis of orthogonal experiments

The aniline simulated wastewater volume for each of the orthogonal experiments was 30 mL. The aniline degradation by hydrogen peroxide alone was examined by adjusting the design of 4 levels (see table 3) for each factor, the initial aniline concentration, the solution pH, the hydrogen peroxide dosage, the reaction time, and the reaction temperature (about 18 ℃) (see tables 4 and 5).

TABLE 3 orthogonal watch head design for aniline degradation by hydrogen peroxide alone

TABLE 4 orthogonal experimental results for aniline degradation by hydrogen peroxide alone

TABLE 5 Quadrature variance analysis Table for aniline degradation by hydrogen peroxide alone

As can be seen from tables 4 and 5, of the five factors (initial concentration of aniline, pH value of solution, dosage of hydrogen peroxide, reaction time, and reaction temperature) affecting the degradation of aniline by hydrogen peroxide alone, the dosage of hydrogen peroxide has the largest influence, the reaction time has the smallest influence, and the degradation rates of aniline are affected in the following order: c is more than A, more than E is more than B, more than D, namely, the adding amount of the hydrogen peroxide is more than the initial concentration of the aniline, more than the reaction temperature (about 18 ℃), more than the pH value of the solution, and more than the reaction time. The factors of economic benefit are comprehensively considered, and the optimized process parameters of all the factors are obtained as follows: aniline initial concentration 30mg/L, pH 6, hydrogen peroxide addition 0.3mL, reaction time 10min, temperature room temperature (about 18 ℃). The analysis result of variance shows that the influence of the adding amount of hydrogen peroxide (factor C) on the degradation rate of the aniline simulation sewage reaches a significant level; while the reaction time (factor D) has minimal effect on the degradation rate and no significance.

Verification experiment

The experiment was repeated three times with 30mL portions of each of 3 aniline simulated wastewater, 30mL portions of each aniline simulated wastewater, an initial aniline concentration of 30mg/L, a pH of 6, an amount of 0.3mL of hydrogen peroxide, a reaction time of 10min, and a room temperature (about 18 ℃) to measure the degradation rates of aniline of 86.4%, 87.6%, and 87.2%, and an average degradation rate of 87.1%, respectively, and it can be seen that the most suitable conditions for degrading aniline by hydrogen peroxide alone were an initial aniline concentration of 30mg/L, a pH of 6, an amount of 0.3mL of hydrogen peroxide, a reaction time of 10min, and a room temperature (about 18 ℃).

Example 7 Effect of Ionic liquid concentration in conjunction with Hydrogen peroxide on the degradation Rate of aniline

6 parts of 30mg/L aniline simulated sewage are prepared, each 30mL aniline simulated sewage is adjusted to have pH of 6, the adding amount of hydrogen peroxide is 0.3mL, the reaction time is 10min, and the influence of the concentrations of the ionic liquid in the sewage, namely 0.2g/L, 0.4g/L, 0.6g/L, 0.8g/L, 1.0g/L and 1.2g/L on the synergistic degradation effect of the ionic liquid of aniline and hydrogen peroxide is examined under the conditions that the reaction temperature is room temperature (about 18 ℃), as shown in FIG. 6.

As shown in FIG. 6, the results show that the degradation rate of aniline increases until the aniline degradation rate is stable with the increase of the concentration of the ionic liquid in the sewage, and the highest degradation rate can reach 96.1%, which is higher than the highest degradation rate of 87.1% for aniline degradation by the action of hydrogen peroxide alone, which indicates that the addition of the ionic liquid and the hydrogen peroxide have synergistic effect. The ionic liquid is added into the solution, so that the degradation rate of the organic matters can be increased.

Verification experiment

Preparing 3 parts of aniline simulated sewage of 30mg/L, each 30mL, adjusting the concentration of ionic liquid in the sewage to be 0.6g/L, adjusting the pH value to be 6, adding 0.3mL of hydrogen peroxide, reacting for 10min, and repeating the experiment for three times under the conditions of room temperature (about 18 ℃), wherein the degradation rates of aniline are respectively 96.0%, 96.2% and 96.0%, and the average degradation rate is 96.1%.

Comparison of two Aniline degradation methods

The degradation conditions of the two methods are comprehensively compared, and the degradation rate of the aniline is determined under respective optimal conditions (namely, the degradation is performed under the conditions that the initial concentration of the aniline is 30mg/L, the pH value is 6, the adding amount of the hydrogen peroxide is 0.3mL, the reaction time is 10min, and the temperature is room temperature (about 18 ℃), the concentration of the ionic liquid and the hydrogen peroxide are 0.6g/L, the pH value is 6, the adding amount of the hydrogen peroxide is 0.3mL, the reaction time is 10min, and the reaction temperature is room temperature (about 18 ℃). (see Table 6)

TABLE 6 comparison of the two degradation methods

As can be seen from Table 6, the ionic liquid and hydrogen peroxide have a good effect of degrading aniline, and the degradation rate can reach 96.1%, which is far higher than 87.1% of the degradation rate of hydrogen peroxide alone on aniline.

Experiments prove that the ionic liquid and the hydrogen peroxide have good degradation rates on organic sewage containing non-chlorinated aromatic compounds such as naphthalene and phenanthrene, chlorinated aromatic compounds, phosphate esters, phthalate esters and phenolic compounds when the concentration of the ionic liquid and the hydrogen peroxide is 0.6g/L, the pH value is 6, the adding amount of the hydrogen peroxide is 0.3mL, the reaction time is 10min, the reaction temperature is room temperature (about 18 ℃), and the initial concentration is 30 g/L.

The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for treating organic matter sewage by using ionic liquid-hydrogen peroxide in a synergistic manner is characterized by comprising the following steps of:

(1) adjusting the pH value of the aniline sewage to 6, adding hydrogen peroxide and ionic liquid into the aniline sewage, standing for 10min, wherein the adding amount of the hydrogen peroxide in the aniline sewage is 1%, the initial concentration of the aniline sewage is 30mg/L, the reaction temperature is 18 ℃, and the concentration of the ionic liquid is 0.6 g/L;

(3) adding an ammonium sulfamate solution into the reaction solution obtained in the step (2), fully oscillating, and standing for 3-5 min;

the ionic liquid is alkyl substituted imidazole ionic liquid.