A method for treating organic wastewater by ferrocene catalyzed discharge low temperature plasma

Abstract

The application discloses a method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, and steps are as follows: putting the organic wastewater into a low-temperature plasma water treatment device, then adding solid ferrocene, and then starting power supply to carry out discharge low-temperature plasma treatment. H2O2 generated by the low-temperature plasma is catalyzed to generate ·OH by ferrocene to degrade organic matters in the wastewater, and meanwhile, the discharge low-temperature plasma process is accompanied by ultraviolet light, so that the catalysis of ferrocene is strengthened. The application has the advantages of simple operation, shortened discharge low-temperature plasma treatment time, good treatment effect of the organic wastewater, and reusable ferrocene as a catalyst.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic pollutant wastewater treatment, and particularly relates to a method for treating organic wastewater by using ferrocene catalytic discharge low-temperature plasma. BACKGROUND

[0002] As a new advanced oxidation technology, low-temperature plasma technology can produce physical effects such as ultraviolet light, high-energy electrons and thermal effects, and oxidizing substances such as ·OH, H2O2 and O3, and has the advantages of short reaction time and less secondary pollution. However, when low-temperature plasma technology is used to treat organic pollutants, the active substances generated by the low-temperature plasma are mainly used to act on the pollutants, and many physical effects generated by the discharge are not fully utilized, so people have been exploring ways to improve the efficiency of low-temperature plasma treatment of wastewater. The common method is to coordinate the plasma with other systems or improve the reactor to improve its efficiency, and the catalytic low-temperature plasma treatment of wastewater is one of the effective means, so it is crucial to find a highly efficient catalyst.

[0003] Ferrocene is an organic transition metal compound with aromatic properties. It is widely used due to its hydrophobicity, stability, low toxicity and biological activity. Due to the high stability of ferrocene and its derivatives in various environments, excellent reversible redox performance and photoelectrochemical activity, they have certain application potential in advanced oxidation catalysis. Current electrochemical research has confirmed that ferrocene can exhibit its reversible redox properties in non-aqueous solvent media and can catalyze the decomposition of H2O2 to generate ·OH.

[0004] In the low-temperature plasma system, the addition of ferrocene can catalyze the reaction to generate more ·OH to treat pollutants, and this reaction is enhanced under the physical effects of low-temperature plasma such as ultraviolet light. Using ferrocene as a catalyst has potential advantages. Ferrocene is insoluble in water and non-toxic, has good chemical stability, and can be easily separated from liquid to achieve recycling effect. Ferrocene is currently produced on a large scale and is cheap and easy to obtain, which is conducive to reducing costs. The discharge low-temperature plasma treatment of organic wastewater can shorten the treatment time and reduce energy consumption. SUMMARY

[0005] In view of the above problems in the prior art, the purpose of the present application is to provide a method for treating organic pollutants by using ferrocene to coordinate low-temperature plasma, which can improve the low energy utilization rate, long reaction time and high cost of the prior art.

[0006] The present application is directed to the above situation, in the low temperature plasma treatment of organic wastewater system, put in solid ferrocene, so as to enhance the low temperature plasma organic sewage treatment capacity. The method is as follows: adding ferrocene in the organic wastewater to be treated, stirring to make it as evenly dispersed as possible, then the low temperature plasma reactor is powered on.

[0007] In order to solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0008] A method for treating organic wastewater by ferrocene catalytic discharge low temperature plasma, comprising the following steps:

[0009] (1) adding solid ferrocene into the organic wastewater;

[0010] (2) putting the organic wastewater containing ferrocene into the discharge low temperature plasma water treatment device, passing in the gas, turning on the power and adjusting the discharge power, and then carrying out low temperature plasma treatment;

[0011] Further, the addition amount of ferrocene in the step (1) is 100 mg / L to 600 mg / L. Preferably, the addition amount of ferrocene in the step (1) is 300 mg / L to 500 mg / L.

[0012] Further, the organic species in the organic wastewater in the step (1) is antibiotics and dyes.

[0013] Further, the organic matter concentration in the organic wastewater in the step (1) is 10 mg / L to 200 mg / L. Preferably, the organic matter concentration in the step (2) is 10 mg / L to 60 mg / L.

[0014] Further, the pH value of the organic wastewater in the step (1) is 3 to 10. Preferably, the pH value of the organic wastewater in the step (1) is 5 to 9.

[0015] Further, the low temperature plasma is generated by pulse high voltage corona discharge.

[0016] Further, the discharge voltage in the step (2) is 19 to 26 kV, and the discharge frequency is 40 to 60 Hz. Preferably, the discharge voltage in the step (2) is 20 to 24 kV, and the discharge frequency is 50 to 60 Hz.

[0017] Further, the gas in the step (2) is air or oxygen. Preferably, the gas in the step (2) is oxygen.

[0018] Further, the low temperature plasma treatment time in the step (2) is 20 minutes to 90 minutes. Preferably, the treatment time in the step (2) is 30 minutes to 60 minutes.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] 1. The low-temperature plasma technology combined with ferrocene catalyst can rapidly generate highly active oxidizing substances such as ·OH, which have strong oxidizing ability and can rapidly degrade organic pollutants. Ferrocene as a catalyst can accelerate the reaction rate and participate in the reaction through multiple mechanisms to promote the degradation process of pollutants, making the treatment process more efficient and rapid.

[0021] 2. Because the generated oxidation products have high oxidizing ability, there are fewer residual products generated during the degradation process, reducing the risk of secondary pollution and being beneficial to the protection of the environment and water resources. Ferrocene is a highly crystalline heterogeneous catalyst that can be used multiple times. Low-temperature plasma technology and ferrocene catalyst are non-toxic and harmless to the environment and will not produce harmful residual substances, which is beneficial to maintaining ecological balance and human health.

[0022] 3. The cost of ferrocene as a catalyst is relatively low and easy to obtain, and the combination with low-temperature plasma technology utilizes multiple mechanisms to improve the treatment efficiency, which has good cost-effectiveness. By fully utilizing the chemical properties of ferrocene and the active substances generated by low-temperature plasma technology, multiple mechanisms are realized, the pollutant degradation capacity is enhanced, and the treatment efficiency is further improved. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 Effect diagram of removing tetracycline in water by ferrocene adsorption alone, low-temperature plasma discharge alone, and ferrocene catalytic low-temperature plasma discharge in Example 1. DETAILED DESCRIPTION

[0024] The specific embodiments of the present application will be further described in detail below in combination with specific examples.

[0025] The numerical ranges in the present application should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each intermediate value within any stated value or stated range, as well as any other stated value or intermediate value within the stated range, is also included in the present application. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0026] Unless otherwise indicated, all technical and scientific terms have the same meaning as those one of ordinary skill in the art of the invention would understand. Although preferred methods and materials are described, 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 herein are incorporated by reference to disclose and describe in detail the methods and / or materials associated with the documents. In the case of conflict between the content of the specification and that of any document incorporated herein by reference, the content of the specification controls. As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", and the like are open-ended terms that are intended to permit but not limit the inclusion of elements or the number of elements, and that do not exclude additional elements or the number of elements.

[0027] The experimental methods used in the present invention are conventional methods unless otherwise specified.

[0028] The materials, reagents, etc. used in the present invention can be purchased or synthesized by known methods unless otherwise specified.

[0029] The quantitative test in the present invention is set up with three repeated experiments, and the average value is taken.

[0030] Example 1

[0031] A method for treating organic wastewater by ferrocene catalytic discharge low-temperature plasma, comprising the following steps:

[0032] (1) adding solid ferrocene into tetracycline organic wastewater, and the ferrocene dosage is 400 mg / L;

[0033] (2) putting the organic wastewater containing ferrocene into a discharge low-temperature plasma water treatment device, and after oxygen is introduced, the power is turned on and the discharge power is adjusted, low-temperature plasma treatment is carried out;

[0034] Tetracycline organic wastewater treatment: the tetracycline wastewater concentration is 50 mg / L, the wastewater pH is 5, the low-temperature plasma discharge voltage is 20 kV, the discharge frequency is 50 Hz, the treatment time is 60 min, the supernatant is taken and the tetracycline concentration before and after the reaction is measured by using a UV spectrophotometer, and the tetracycline removal rate can reach 75.99%.

[0035] Example 2

[0036] A method for treating organic wastewater by ferrocene catalytic discharge low-temperature plasma, comprising the following steps:

[0037] The ferrocene dosage is 300 mg / L, and the other conditions are the same as those in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment reaches 72.76%.

[0038] Example 3

[0039] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0040] The ferrocene dosage is 500 mg / L, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment reaches 74.38%, which is increased by 14.31% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0041] Example 4

[0042] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0043] The discharge voltage of the low-temperature plasma is 24 kV, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment reaches 82.62%, which is increased by 22.55% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0044] Example 5

[0045] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0046] The solution pH is 5, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment is increased by 12.93% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0047] Example 6

[0048] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0049] The solution pH is 9, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment is increased by 9.57% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0050] Example 7

[0051] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0052] The discharge frequency is 60 Hz, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the tetracycline removal rate after treatment reaches 79.46%, which is increased by 19.39% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0053] Example 8

[0054] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0055] The tetracycline wastewater concentration is 60 mg / L, and other conditions are the same as in Example 1. The tetracycline wastewater is treated, and the removal rate of tetracycline after treatment reaches 77.83%, which is increased by 14.29% compared with the single discharge low-temperature plasma treatment under the same conditions.

[0056] Example 9

[0057] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0058] (1) solid ferrocene is added to brilliant yellow dye wastewater, and the ferrocene dosage is 400 mg / L;

[0059] (2) the brilliant yellow dye wastewater containing ferrocene is put into a discharge low-temperature plasma water treatment device, oxygen is introduced, the power is turned on and the discharge power is adjusted, and then low-temperature plasma treatment is carried out;

[0060] Brilliant yellow dye wastewater treatment: the brilliant yellow dye wastewater concentration is 50 mg / L, the wastewater pH is 6.21, the low-temperature plasma discharge voltage is 25 kV, the discharge frequency is 50 Hz, the treatment time is 30 min, the supernatant is taken, and the brilliant yellow concentration before and after the reaction is measured by using a UV spectrophotometer, and the brilliant yellow removal rate can reach 70.18%, which is increased by 23.80% compared with the single discharge low-temperature plasma treatment under the same conditions.

[0061] Example 10

[0062] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0063] (1) solid ferrocene is added to brilliant yellow dye wastewater, and the ferrocene dosage is 400 mg / L;

[0064] (2) the brilliant yellow dye wastewater containing ferrocene is put into a discharge low-temperature plasma water treatment device, oxygen is introduced, the power is turned on and the discharge power is adjusted, and then low-temperature plasma treatment is carried out;

[0065] Brilliant yellow dye wastewater treatment: the brilliant yellow dye wastewater concentration is 50 mg / L, the wastewater pH is 6.21, the low-temperature plasma discharge voltage is 25 kV, the discharge frequency is 50 Hz, the treatment time is 30 min, the supernatant is taken, and the brilliant yellow concentration before and after the reaction is measured by using a UV spectrophotometer, and the brilliant yellow removal rate can reach 70.18%, which is increased by 23.80% compared with the single discharge low-temperature plasma treatment under the same conditions.

[0066] Example 11

[0067] A method for treating organic wastewater by ferrocene catalyzed discharge low-temperature plasma, comprising the following steps:

[0068] (1) adding solid ferrocene into the alizarin dye wastewater, the ferrocene dosage is 400 mg / L;

[0069] (2) putting the alizarin dye wastewater containing ferrocene into the discharge low-temperature plasma water treatment device, passing in gas, turning on the power and adjusting the discharge power, and then performing low-temperature plasma treatment;

[0070] Alizarin dye wastewater treatment: the alizarin dye wastewater concentration is 50 mg / L, the wastewater pH is 8.06, the low-temperature plasma discharge voltage is 25 kV, the discharge frequency is 50 Hz, the treatment time is 30 min, the supernatant is taken, and the alizarin concentration before and after the reaction is measured by using an ultraviolet spectrophotometer, and the alizarin removal rate can reach 80.12%, which is increased by 29.16% compared with the discharge low-temperature plasma treatment alone under the same conditions.

[0071] Example 12

[0072] A method for treating organic wastewater by ferrocene catalytic discharge low-temperature plasma, comprising the following steps:

[0073] (1) adding solid ferrocene into the alizarin dye wastewater, the ferrocene dosage is 400 mg / L;

[0074] (2) putting the alizarin dye wastewater containing ferrocene into the discharge low-temperature plasma water treatment device, passing in gas, turning on the power and adjusting the discharge power, and then performing low-temperature plasma treatment;

[0075] Crystal violet dye wastewater treatment: the crystal violet dye wastewater concentration is 50 mg / L, the wastewater pH is 6.03, the low-temperature plasma discharge voltage is 25 kV, the discharge frequency is 50 Hz, the treatment time is 30 min, the supernatant is taken, and the crystal violet concentration before and after the reaction is measured by using an ultraviolet spectrophotometer, and the crystal violet removal rate can reach 65.53%, which is increased by 16.09% compared with the discharge low-temperature plasma treatment alone under the same conditions.

Claims

1. A method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma, characterized in that, Includes the following steps: (1) Add solid ferrocene to organic wastewater; (2) The organic wastewater containing ferrocene is placed into the discharge low-temperature plasma water treatment device, gas is introduced, the power is turned on and the discharge power is adjusted, and then low-temperature plasma treatment is carried out.

2. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, In step (1), the dosage of ferrocene is 100 mg / L to 600 mg / L.

3. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, The organic substances in the organic wastewater in step (1) are antibiotics and dyes.

4. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, In step (1), the concentration of organic matter in the organic wastewater is 10 mg / L to 200 mg / L.

5. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, In step (1), the pH value of the organic wastewater is 3 to 10.

6. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, The low-temperature plasma is generated by pulsed high-voltage corona discharge.

7. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, In step (2), the discharge voltage is 19-26kV and the discharge frequency is 40-60Hz.

8. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, The gas in step (2) is air or oxygen.

9. The method for treating organic wastewater using ferrocene catalytic discharge low-temperature plasma according to claim 1, characterized in that, The low-temperature plasma treatment time in step (2) is 20 to 90 minutes.

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