METHOD FOR IN-SITU GENERATION OF NANOFLOWER-LIKE MANGANESE DIOXIDE CATALYST ON FILTER MATERIAL

Abstract

This present invention discloses method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material. The method comprises: immersing a filter material in a solution containing sodium lauryl sulfate and nitric acid; first modifying the surface of the filter material by using the sodium lauryl sulfate so that a charge layer is wound around the surface of the filter material and tightly absorbs H.sup.+ in an acid solution; and then adding potassium permanganate as an oxidant to react with H.sup.+ on the surface of the filter material to generate nano flower-like manganese dioxide in situ on the surface of the filter material, so as to obtain a composite filter material having a denitration function. Since the surface of the filter fiber is uniformly coated with a layer of nanoflower-like manganese dioxide, the manganese dioxide of such a morphology has a larger specific surface area and a higher pore volume than ordinary manganese dioxide, and is more conducive to the diffusion of the reaction gas, and therefore the catalytic filter material has very excellent low-temperature activity, the NOx removal efficiency reach 97% at 160 C., and the composite filter material has excellent bonding strength, gas permeability and catalytic stability. In addition, the method is environmentally friendly, reagents used in the experiment are cheap and readily available, and the experimental process is easy to operate, and the reaction process takes only 2-3 hours; therefore, the method is advantageous for large-scale experimental production.

Claims

1. Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material, comprising the steps of: immersing a filter material in a solution containing sodium lauryl sulfate and nitric acid; first modifying the surface of the filter material by using the sodium lauryl sulfate so that a charge layer is wound around the surface of the filter material and sufficiently absorbs H.sup.+ in the solution; and then adding potassium permanganate to the solution to react with H.sup.+ on the surface of the filter material to generate nano flower-like manganese dioxide in situ on the surface of the filter material, so as to obtain a composite filter material having a denitration function.

2. The method as claimed in claim 1, wherein the concentration of sodium lauryl sulfate is 0.1-2 g/L and the concentration of nitric acid is 0.01-0.2 M in the solution.

3. The method as claimed in claim 1, wherein the filter material is a polyphenylene sulfide needle felt filter material.

4. The method as claimed in claim 1, specifically comprising the following preparation steps: 1) immersing a filter material in a solution containing sodium lauryl sulfate and nitric acid, and dispersing for 1 h by using ultrasonic waves so that the sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material; 2) after the reaction solution of step 1) is heated to 60-80 C., adding potassium permanganate and further stirring for reaction for 0.5-2 h so that the potassium permanganate reacts with H.sup.+ on the surface of the filter material to generate nano flower-like manganese oxide in situ; and 3) rinsing the filter material obtained in step 2) with deionized water and ethanol, and drying it in a vacuum oven at 110 C. for 6b to obtain a composite filter material with a denitration function.

5. The method as claimed in claim 4, wherein the concentration of potassium permanganate in the reaction system of Step 2) is 0.01-0.2M.

6. A filter material prepared by the method claimed in claim 1, wherein the filter material is used for removing PM2.5 and NO.sub.x simultaneously.

7. A filter material claimed in claim 6, wherein the concentration of sodium lauryl sulfate is 0.1-2 g/L and the concentration of nitric acid is 0.01-0.2 M in the solution.

8. A filter material claimed in claim 6, wherein the filter material is a polyphenylene sulfide needle felt filter material.

9. A filter material claimed in claim 6, wherein the specifically comprising the following preparation steps: 1) immersing a filter material in a solution containing sodium lauryl sulfate and nitric acid, and dispersing for 1 h by using ultrasonic waves so that the sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material; 2) after the reaction solution of step 1 is heated to 60-80 C. adding potassium permanganate and further stirring for reaction for 0.5-2 h so that the potassium permanganate reacts with H.sup.+ on the surface of the filter material to generate nano flower-like manganese oxide in situ; and 3) rinsing the filter material obtained in step 2) with deionized water and ethanol, and drying it in a vacuum oven at 110 C. for 6 h to obtain a composite filter material with a denitration function.

10. A filter material claimed in claim 9, wherein the concentration of potassium permanganate in the reaction system of Step 2) is 0.01-0.2M.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1 shows SEM diagrams of raw polyphenylene sulfide needle felt filter materials (A, B) and polyphenylene sulfide composite filter materials with a denitration function (C, D);

[0021] FIG. 2 shows TEM diagrams of a raw polyphenylene sulfide needle felt filter material (A) and polyphenylene sulfide composite filter materials with a denitration function (B, C), and an EDX diagram (D) of a polyphenylene sulfide composite filter material with a denitration function;

[0022] FIG. 3 shows analysis of the surface element composition of a polyphenylene sulfide composite filter fiber with a denitration function;

[0023] FIG. 4 is a diagram showing the NO conversion rate of the polyphenylene sulfide composite filter having a denitration function at 160 C.;

[0024] FIG. 5 shows the bonding strength of the polyphenylene sulfide composite filter with a denitration function;

[0025] FIG. 6 shows the gas permeability of the raw polyphenylene sulfide needle felt filter material and the polyphenylene sulfide composite filter material with a denitration function.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] In order to make the objects, technical solutions, and advantages of the present invention more comprehensible, the present invention will be further described in detail below in conjunction with the embodiments. It should be understood that specific embodiments described here are merely illustrative of the present invention rather than limiting it. The application principle of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

Embodiment 1

[0027] Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material, comprising the following steps:

[0028] a) adding 0.042 g of sodium dodecyl sulfate solid particles and a trace of concentrated nitric acid to deionized water, stirring and dissolving to prepare a sodium dodecyl sulfate solution with a concentration of 0.84 g/L, wherein the concentration of nitric acid is controlled to be 0.05M;

[0029] b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;

[0030] c) heating the reaction system to 70 C., adding a potassium permanganate solution dropwise with a concentration of 0.05M and further stirring for reaction for 1.5 h so that the potassium permanganate reacts with H on the surface of the filter material to generate nano flower-like manganese oxide in situ; and

[0031] d) rinsing the filter material obtained in Step c) with deionized water and ethanol, and drying in a vacuum oven at 110 C. for 6 h to obtain a composite filter material having a denitration function.

[0032] The denitration performance of the composite filter material is evaluated in a self-made tubular SCR reactor. Test conditions: [NO][NH.sub.3]=400 ppm, [O.sub.2]=5%, N.sub.2 is equilibrium gas, the gas flow rate is 700 mL*min.sup.1, the temperature is set to 160 C., and the denitration efficiency measured with a British KM940 flue gas analyzer is 97%.

Embodiment 2

[0033] Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material, comprising the following steps:

[0034] a) adding 0.024 g of sodium dodecyl sulfate solid particles and a trace of concentrated nitric acid to deionized water, stirring and dissolving to prepare a sodium dodecyl sulfate solution with a concentration of 0.48 g/L, wherein the concentration of nitric acid is controlled to be 0.1 M;

[0035] b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;

[0036] c) heating the reaction system to 80 C., adding a potassium permanganate solution dropwise with a concentration of 0.1M and further stirring for reaction for 2 h so that the potassium permanganate reacts with H.sup.+ on the surface of the filter material to generate nano flower-like manganese oxide in situ; and

[0037] d) rinsing the filter material obtained in Step c) with deionized water and ethanol, and drying in a vacuum oven at 110 C. for 6 h to obtain a composite filter material having a denitration function.

[0038] The denitration performance of the composite filter material is evaluated in a self-made tubular SCR reactor. Test conditions: [NO][NH.sub.3]=400 ppm, [O.sub.2]=5%, N.sub.2 is equilibrium gas, the gas flow rate is 700 mL.Math.min.sup.1, the temperature is set to 160 C., and the denitration efficiency measured with a British KM940 flue gas analyzer is 100%.

Embodiment 3

[0039] Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material, comprising the following steps:

[0040] a) adding 0.042 g of sodium dodecyl sulfate solid particles and a trace of concentrated nitric acid to deionized water, stirring and dissolving to prepare a sodium dodecyl sulfate solution with a concentration of 0.84 g/L, wherein the concentration of nitric acid is controlled to be 0.02M;

[0041] b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;

[0042] c) heating the reaction system to 65 C., adding a potassium permanganate solution dropwise with a concentration of 0.02M and further stirring for reaction for 1.5 h so that the potassium permanganate reacts with H.sup.+ on the surface of the filter material to generate nano flower-like manganese oxide in situ; and

[0043] d) rinsing the filter material obtained in Step c) with deionized water and ethanol, and drying in a vacuum oven at 110 C. for 6 h to obtain a composite filter material having a denitration function.

[0044] The denitration performance of the composite filter material is evaluated in a self-made tubular SCR reactor. Test conditions: [NO][NH.sub.3]=400 ppm, [O.sub.2]=5%, N.sub.2 is equilibrium gas, the gas flow rate is 700 mL*min-1, the temperature is set to 160 C., and the denitration efficiency measured with a British KM940 flue gas analyzer is 95%.

Embodiment 4

[0045] Method for in-situ generation of nanoflower-like manganese dioxide catalyst on filter material, comprising the following steps:

[0046] a) adding 0.042 g of sodium dodecyl sulfate solid particles and a trace of concentrated nitric acid to deionized water, stirring and dissolving to prepare a sodium dodecyl sulfate solution with a concentration of 0.84 g/L, wherein the concentration of nitric acid is controlled to be 0.05M;

[0047] b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;

[0048] c) heating the reaction system to 65 C., adding a potassium permanganate solution dropwise with a concentration of 0.05M and further stirring for reaction for 2.5 h so that the potassium permanganate reacts with H.sup.+ on the surface of the filter material to generate nano flower-like manganese oxide in situ; and

[0049] d) rinsing the filter material obtained in Step c) with deionized water and ethanol, and drying it in a vacuum oven at 110 C. for 6 h to obtain a composite filter material having a denitration function.

[0050] The denitration performance of the composite filter material is evaluated in a self-made tubular SCR reactor. Test conditions: [NO][NH.sub.3]=400 ppm, [Oz]=5%, N.sub.2 is equilibrium gas, the gas flow rate is 700 mL*min.sup.1, the temperature is set to 160 C., and the denitration efficiency measured with a British KM940 flue gas analyzer is 96%.

[0051] The embodiments mentioned above are merely preferred embodiments of the present invention and not intended to limit the present invention. Any of modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention shall be covered in the protection scope of the present invention.