A method for degrading phenolic compounds in water

Abstract

This invention belongs to the field of phenol-containing wastewater treatment technology, and relates to a method for degrading phenolic compounds in water. Al₂O₃ is added to water containing phenolic compounds, mixed thoroughly, and then KMnO₄ is added to degrade the phenolic compounds; alternatively, Al₂O₃ and KMnO₄ are mixed thoroughly and then added to water containing phenolic compounds to degrade them. The Al₂O₃ catalyst prepared by this invention is prepared at a relatively low temperature, the preparation process is simple and easy to learn, and the raw materials are inexpensive and readily available. During the degradation of phenolic compounds in water, it was found that the addition of Al₂O₃ significantly promoted the rate and efficiency of KMnO₄ solution oxidation in removing various phenolic compounds, and the reaction rate of the KMnO₄ / Al₂O₃ system increased by 1.5 to 20 times compared to the KMnO₄ degradation system alone. The KMnO₄ / Al₂O₃ fixed-bed reactor of this invention can treat phenol-containing wastewater and can be widely applied in industry, with a daily treatment capacity of over 3.6 L / h.

Description

Technical Field

[0001] This invention belongs to the field of phenol-containing wastewater treatment technology, and relates to a method for degrading phenolic compounds in water. Background Technology

[0002] Potassium permanganate (KMnO4) is considered a promising oxidant due to its advantages such as high efficiency, low cost, and relative stability. [1-3] However, the stability of KMnO4 may hinder the treatment efficiency of pollutants in homogeneous systems to some extent. To address this deficiency, researchers have improved the oxidation capacity of KMnO4 by adding solid catalysts. Currently available solid catalysts include graphite. [1] Ru / TiO2 [4] Biochar [5-6] and carbon nanotubes [7] KMnO4 can efficiently degrade organic pollutants, including sulfamethoxazole, through adsorption of target compounds to form a pollutant-catalyst interface. However, these materials suffer from inherent drawbacks such as high cost and short reaction time, hindering their application in environmental technologies. Furthermore, the feasibility and general applicability of the proposed technologies for industrial use remain unknown. Therefore, it is necessary to explore other efficient, low-cost, and recyclable catalysts to improve the performance of the KMnO4 oxidation system.

[0003] Alumina (Al2O3) is widely used as a carrier material for the efficient catalytic degradation of pollutants due to its low price and high specific surface area. [8-11] At present, KMnO4 impregnated Al2O3 particles It exhibits excellent performance in industrial applications and can be used to remove waste gases such as hydrogen sulfide (H2S), sulfur dioxide (SO2), and nitrogen dioxide (NO2).

[12] However, there are currently no other similar commercial products used for the treatment of water pollutants, and this gap in the field urgently needs to be filled. Summary of the Invention

[0004] The technical problem this invention aims to solve is to address the shortcomings of existing technologies by providing a catalytic technology for improving the oxidation efficiency of KMnO4 using Al2O3 prepared by a simple method. The Al2O3 raw material used in this invention is inexpensive, the preparation process is simple and easy to implement, and the resulting Al2O3 catalyst exhibits excellent characteristics of high efficiency, stability, and recyclability. The method provided by this invention can achieve efficient treatment of various phenols and can be designed as a fixed-bed catalyst for the treatment and widespread application of industrial wastewater.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0006] This invention discloses a method for degrading phenolic compounds in water by adding Al2O3 and KMnO4 to water containing phenolic compounds to degrade the phenolic compounds.

[0007] In some embodiments, Al2O3 is added to water containing phenolic compounds, mixed well, and then KMnO4 is added to degrade the phenolic compounds; or, Al2O3 and KMnO4 are mixed well and then added to water containing phenolic compounds to degrade the phenolic compounds.

[0008] In some embodiments, the phenolic compound is phenol, 2,4-dichlorophenol (2,4-DCP), 2,4-dibromophenol (2,4-DBP), 2,4-difluorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, pentabromophenol, nonylphenol, chlorobenzylphenol, bisphenol A, bisphenol B, bisphenol S, benzophenone-1, benzophenone-4, or benzophenone-8.

[0009] In some embodiments, the water containing phenolic compounds needs to be pretreated by adding sodium hydroxide to the water. The amount of sodium hydroxide added is sufficient to dissolve the phenolic compounds in the water. However, if all the phenolic compounds in the water have already dissolved, it is not necessary to add sodium hydroxide. Adding sodium hydroxide is to aid in the dissolution of the phenolic compounds.

[0010] In some embodiments, the concentration of phenolic compounds in the water body ranges from 2.0 μmol / L to 2.0 mmol / L.

[0011] In some embodiments, the KMnO4 is added as an aqueous solution of KMnO4.

[0012] The amount of water used in the KMnO4 aqueous solution is based on the water's ability to dissolve the KMnO4, and there is no concentration limit for the KMnO4 aqueous solution.

[0013] In some embodiments, the molar ratio of the phenolic compound to KMnO4 is 1:0.5 to 20, preferably 1:2 to 20; the molar mass ratio of the phenolic compound to Al2O3 is 0.01 mmol:0.1 g to 2 g, preferably 0.01 mmol:1 g; the degradation reaction is carried out at a temperature of 24°C to 26°C and a reaction time of 10 to 120 min, preferably 20 min.

[0014] In some embodiments, the degradation reaction is carried out in the pH range of 5 to 10, preferably pH 6 to 8, and more preferably pH 7.

[0015] In this process, an acid or alkali is added to the water containing phenolic compounds to adjust the pH to 5-10, and then the water is mixed with KMnO4 to carry out a degradation reaction; the acid is hydrochloric acid; and the alkali is sodium hydroxide.

[0016] In some embodiments, the degradation of phenolic compounds is carried out using a conventional reactor or a fixed-bed reactor.

[0017] Since KMnO4 alone can undergo oxidation upon contact with phenolic compounds, to understand and ensure that Al2O3 plays a catalytic role throughout the reaction process, when using a conventional reactor, Al2O3 is added before KMnO4 contacts the phenolic compounds, or Al2O3 and KMnO4 are contacted first, followed by contact with the phenolic compounds. However, when using a fixed-bed reactor, since both phenolic compounds and KMnO4 are added in solution form, the water containing phenolic compounds is mixed with the KMnO4 aqueous solution and passed through the Al2O3 fixed bed in a short time. In this case, the contact time between phenolic compounds and KMnO4 is negligible compared to the actual treatment time using a conventional reactor.

[0018] In some embodiments, when a fixed-bed reactor is used, Al2O3 is placed in the fixed bed, and water penetrates the fixed bed to carry out the degradation reaction.

[0019] In some embodiments, the Al2O3 is prepared by the following method: aluminum nitrate nonahydrate (Al(NO3)3·9H2O) is placed in a crucible, the crucible is heated, and heating is stopped after the water in the crucible evaporates. The solid with evaporated water in the crucible is collected. The solid with evaporated water is placed in a quartz tube of a tube furnace for calcination. After calcination, it is cooled and ground to obtain the final product.

[0020] The heating crucible is heated to a temperature of 150°C.

[0021] The calcination is carried out in an air atmosphere at a temperature of 300°C for 1 hour.

[0022] Beneficial effects:

[0023] (1) The Al2O3 catalyst prepared by this invention is prepared at a relatively low temperature. The preparation process is simple and easy to learn, and the raw materials are cheap and readily available.

[0024] (2) During the degradation of phenolic compounds in water, it was found that the addition of Al2O3 significantly promoted the rate and efficiency of the oxidation and removal of various phenolic compounds by KMnO4 solution. The reaction rate of the KMnO4 / Al2O3 system increased by 1.5 to 20 times compared with the KMnO4 degradation system alone.

[0025] (3) The KMnO4 / Al2O3 fixed bed reactor of the present invention can treat phenol-containing wastewater and is widely used in industry. Its daily treatment capacity can reach more than 3.6L / h. Attached Figure Description

[0026] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0027] Figure 1 This is a scanning electron microscope image of the Al2O3 catalyst in Example 1.

[0028] Figure 2 The images show the X-ray diffraction pattern and the X-ray photoelectron spectrum; among them, Figure 2 A is the X-ray diffraction pattern of the Al2O3 catalyst; Figure 2 B is the X-ray photoelectron spectrum (XPS) of N1s; Figure 2 C represents the XPS spectrum of Al 2p; Figure 2 D is the XPS spectrum of O1s.

[0029] Figure 3 The graph shows the performance of Al2O3 catalyst in catalyzing the degradation of phenolic compounds by KMnO4.

[0030] Figure 4 These are the relevant experimental diagrams from Examples 3 and 4; wherein, Figure 4 A is a graph showing the recyclability of Al2O3-catalyzed KMnO4 oxidation of 2,4-DCP; Figure 4 B is a schematic diagram of a fixed bed; Figure 4 C represents the degradation efficiency of 2,4-DBP in a KMnO4 / Al2O3 fixed-bed reactor. Figure 4 The red text in C indicates the molar ratio of [2,4-DBP] and [KMnO4]; Figure 4 D represents the reusable experiment diagram for the fixed-bed reactor. Figure 4 The molar ratio of [2,4-DBP] and [KMnO4] in D is indicated in blue. Detailed Implementation

[0031] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0032] In this embodiment of the invention, the pH of the degradation reaction solution is adjusted by adding hydrochloric acid or sodium hydroxide.

[0033] Example 1: Preparation of Al2O3 catalyst

[0034] 108.9 g of Al(NO3)3·9H2O was placed in a crucible and heated at 150 °C. Under these conditions, the solid Al(NO3)3·9H2O in the crucible first turned into a liquid, and then the water gradually evaporated. When it turned into a white solid, heating was stopped and the white solid that had evaporated all the water was collected from the crucible. This white solid spontaneously absorbs water, so the collected solid was quickly placed into a quartz tube in a tube furnace and calcined at 300 °C in air for 1 hour. Calcination was complete when no more brownish-red gas was observed emanating from the quartz tube. After calcination, the solid was cooled and ground to obtain 50.0 g of Al2O3 catalyst.

[0035] Figure 1 The image shows a scanning electron microscope (SEM) image of the Al2O3 catalyst. As can be seen from the image, the synthesized Al2O3 has an irregular shape, a rough surface, some small pores, and small particles with a particle size of about 5 μm.

[0036] Figure 2 A is the X-ray diffraction (XRD) pattern of the Al2O3 catalyst. The XRD pattern of the thermally synthesized Al2O3 shows a distinct broad peak at 24.5°. According to the card, this peak belongs to the aluminum hydroxide (Al(OH)3) phase (JCPDS#37-1377), which is generally present in mixtures formed by Al2O3 and Al(OH)3 at 200–450°C. The peak at 64.9° is likely caused by the presence of the zeolite phase (AlO(OH)) (JCPDS#83-2384) and Al(OH)3.

[0037] Figure 2 B is the X-ray photoelectron spectrum (XPS) of N1s; Figure 2 C represents the XPS spectrum of Al 2p; Figure 2 D is the XPS spectrum of O1s. Figure 2 The N1s spectrum of Al2O3 in B contains three fitted peaks located at 407.1 eV, 402.0 eV, and 397.2 eV. The peak at a binding energy (BE) of 407.1 eV is typically associated with NO2 species bound to different surface oxygen sites. The peak at 402.0 eV is considered to be a weakly physi-adsorbed N species on the surface. The other peak at BE of 397.2 eV is attributed to AlN species formed by N-Al bonding. In the Al 2p and O1s spectra, two sets of peaks at 74.1 eV and 531.2 eV, and at 75.4 eV and 532.7 eV, are associated with Al2O3 and (Al)-OH, respectively. Figure 2 C Figure 2 D). Figure 2The XPS results show that Al2O3 was successfully synthesized, and a small amount of N was incorporated into the synthesized Al2O3.

[0038] Example 2: Degradation of phenolic compounds using a conventional reactor

[0039] (1) Weigh 0.0326 g of 2,4-DCP (0.2 mmol), add 200 μL of 2.0 M sodium hydroxide aqueous solution (0.4 mmol) to aid dissolution, then add deionized water to dissolve, and finally dilute to 100.0 mL in a volumetric flask to obtain a 2.0 mM 2,4-DCP stock solution.

[0040] (2) Weigh 0.079 g KMnO4 solid (0.5 mmol), dissolve it in deionized water, and dilute to 10.0 mM KMnO4 solution in a 50.0 mL volumetric flask and store it in the dark.

[0041] (3) Mix 0.12 g Al2O3, 600.0 μL 2.0 mM 2,4-DCP stock solution (prepared in step 1) and 40.0 mL deionized water to obtain a mixed solution. Adjust the pH of the mixed solution to 7, the concentration of Al2O3 in the mixed solution to 3 g / L, and the concentration of 2,4-DCP in the mixed solution to 30.0 μM. Then add 360.0 μL KMnO4 solution (0.0036 mmol KMnO4, prepared in step 2) to the mixed solution containing Al2O3 and 2,4-DCP to obtain a degradation reaction solution. Perform the degradation reaction by magnetic stirring at 25 °C for 20 min. Monitor the change in the concentration of 2,4-DCP using high performance liquid chromatography and calculate its degradation rate.

[0042] For suspensions containing Al2O3, centrifugation is used to separate the solid and liquid phases. The resulting Al2O3 is then washed and dried to obtain recyclable Al2O3.

[0043] The experiment was repeated by replacing 2,4-DCP in the above KMnO4 / Al2O3 degradation system with phenol, 2,4-DBP, 2,4-difluorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, pentabromophenol, nonylphenol, chlorobenzylphenol, bisphenol A, bisphenol B, bisphenol S, benzophenone-1, benzophenone-4, and benzophenone-8.

[0044] Comparative Example 1: Degradation of phenolic compounds by KMnO4 alone

[0045] (1) Weigh 0.0326 g of 2,4-DCP (0.2 mmol), add 200 μL of 2.0 M sodium hydroxide aqueous solution (0.4 mmol) to aid dissolution, then add deionized water to dissolve, and finally dilute to 100.0 mL in a volumetric flask to obtain a 2.0 mM 2,4-DCP stock solution.

[0046] (2) Weigh 0.079 g KMnO4 solid (0.5 mmol), dissolve it in deionized water, and dilute to 10.0 mM KMnO4 solution in a 50.0 mL volumetric flask and store it in the dark.

[0047] (3) Mix 600.0 μL of 2.0 mM 2,4-DCP stock solution (prepared in step 1) and 40.0 mL of deionized water to obtain a mixed solution. Adjust the pH of the mixed solution to 7 and the concentration of 2,4-DCP in the mixed solution to 30.0 μM. Then add 360.0 μL of KMnO4 solution (0.0036 mmol KMnO4, prepared in step 2) to the mixed solution containing 2,4-DCP to obtain a degradation reaction solution. Perform the degradation reaction by magnetic stirring at 25 °C for 20 min. Monitor the change in the concentration of 2,4-DCP using high performance liquid chromatography and calculate its degradation rate.

[0048] The experiment was repeated by replacing 2,4-DCP in the above-mentioned KMnO4 degradation system with phenol, 2,4-DBP, 2,4-difluorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, pentabromophenol, nonylphenol, chlorobenzylphenol, bisphenol A, bisphenol B, bisphenol S, benzophenone-1, benzophenone-4, and benzophenone-8.

[0049] Example 3

[0050] (1) Analysis of the degradation results of phenolic pollutants by different catalytic systems

[0051] The degradation performance of phenolic compounds in Example 2 and Comparative Example 1 is shown in the graphs. Figure 3 As shown, Figure 3 A shows the performance of the KMnO4 / Al2O3 system and the KMnO4 system alone in the degradation of 2,4-DCP. The performance of the degradation of phenol, 2,4-DBP, 2,4-difluorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, pentabromophenol, nonylphenol, chlorobenzylphenol, bisphenol A, bisphenol B, bisphenol S, benzophenone-1, benzophenone-4, and benzophenone-8 is shown in the figure. Figure 3 B~ Figure 3 As shown in F.

[0052] from Figure 3It can be seen that, under the same reaction conditions, the degradation process of the above-mentioned phenolic pollutants is promoted in the presence of Al2O3 compared to the KMnO4 system alone.

[0053] (2) Analysis of the recyclability of Al2O3-catalyzed KMnO4 oxidation of 2,4-DCP

[0054] The reaction solution was centrifuged, and the resulting Al2O3 was washed and dried. The Al2O3 was then recycled to catalyze the degradation of 2,4-DCP.

[0055] Figure 4 A is a graph showing the recyclability of Al2O3 catalyzing the oxidation of 2,4-DCP by KMnO4. The reaction conditions were [2,4-DCP]0 = 30.0 μM, [KMnO4]0 = 90.0 μM, [Al2O3]0 = 3.2 g / L, T = 25.0℃, and pH = 7. Under these conditions, after Al2O3 had been recycled four times, it could still catalyze the removal of 74% of 2,4-DCP by KMnO4 within 10 minutes, with a catalytic efficiency of 79% of that of the original Al2O3.

[0056] Example 4: Degradation reaction using a fixed-bed reactor

[0057] (1) Degradation efficiency of KMnO4 / Al2O3 fixed-bed reactor

[0058] Fixed-bed reactors, such as Figure 4 As shown in Figure B, the fixed-bed equipment dimensions are 300 mm (diameter) × 100.0 mm (height), with an Al2O3 catalyst packing height of 50.0 mm. Catalytic degradation was performed using 2,4-DBP as the model compound.

[0059] KMnO4 solution and 2,4-DBP solution were simultaneously pumped into a fixed bed filled with Al2O3 catalyst at equal flow rates using a pumping device. The total flow rate of the mixture was 60.0 mL / min, meaning the flow rates of the KMnO4 solution and the 2,4-DBP solution were each 30.0 mL / min. Immediately after mixing, the KMnO4 solution and the 2,4-DBP solution came into contact with Al2O3 (the two solutions passed through the Al2O3 fixed bed very quickly after contact). After degradation, the reaction solution flowed out from the bottom outlet of the fixed bed reactor, thus achieving the purpose of treating phenol-containing wastewater.

[0060] Figure 4 C represents the degradation efficiency of 2,4-DBP in a KMnO4 / Al2O3 fixed-bed reactor. Figure 4In section C, the red text indicates the molar ratio of [2,4-DBP] to [KMnO4]. The reaction conditions are: after mixing KMnO4 solution and 2,4-DBP solution, the [2,4-DBP]0 in the mixture is 30.0 μM, and the molar ratio of [2,4-DBP]0 : [KMnO4]0 is 1:0.5, 1:1, 1:2, and 1:3. V (Al2O3) =3532.50cm 3 The flow rate of the mixed solution was v = 60.0 mL / min, and the flow rate ratio of KMnO4 solution to 2,4-DBP solution was 1:1; Figure 4 As shown in Figure C, the concentration of 2,4-DBP significantly decreased after passing through the Al2O3-filled fixed bed. When the KMnO4 concentration increased to 60.0 μM or higher, the removal rate of 2,4-DBP reached 3.6 L / h. Furthermore, when the flow rate increased to 120.0 mL / min, 60.0 μM KMnO4 could completely remove 2,4-DBP (30.0 μM) within 6.0 h. Therefore, increasing the oxidant dosage or flow rate can further improve the daily treatment capacity of the fixed-bed reactor. The effluent from the fixed bed is colorless, so there is no need to worry about color issues caused by KMnO4.

[0061] (2) Recycling degradation capacity of KMnO4 / Al2O3 fixed-bed reactor

[0062] To verify the circulation capacity of the fixed bed, a scaled-down fixed bed (with low water consumption under laboratory conditions) was set up in the test. Its specific dimensions were 26.0 mm (diameter) × 125.0 mm (height). Al2O3 was still filled to a height of 50.0 mm, and the total flow rate of the mixed liquid was reduced to 0.25 mL / min.

[0063] Figure 4 D represents the recycling experiment test of the fixed-bed reactor. Figure 4 The molar ratio of [2,4-DBP] to [KMnO4] in D is indicated in blue. The reaction conditions are: after mixing KMnO4 solution and 2,4-DBP solution, the [2,4-DBP]0 in the mixture is 30.0 μM, and the molar ratio of [2,4-DBP]0:[KMnO4]0 is 1:0.5, 1:1, 1:2 and 1:3, V (Al2O3) =26.53cm 3 The flow rate was v = 0.25 mL / min, and the flow rate ratio of KMnO4 solution to 2,4-DBP solution was 1:1. Figure 4As shown in Figure D, under high oxidant dosages ([2,4-DBP]:[KMnO4] molar ratio of 1:2 or 1:3), the degradation efficiency of 2,4-DBP did not significantly decrease within 10 cycles (each cycle lasting 20 minutes, adjusted by controlling the flow rate of the mixed solution to ensure a cycle time similar to that of a conventional reactor). This indicates that the reactor exhibits good recycling performance. These results suggest that the fixed-bed treatment system based on KMnO4 / Al2O3 oxidation has certain application potential and can be considered for the removal of phenolic substances from industrial wastewater.

[0064] This invention provides a method for degrading phenolic compounds in water. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

[0065] References:

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Claims

1. A method for degrading phenolic compounds in a body of water, characterized by, Al2O3 and KMnO4 are added to a water body containing phenolic compounds to degrade the phenolic compounds; The Al2O3 is prepared by placing aluminum nitrate nonahydrate in a crucible, heating the crucible, stopping heating when the water in the crucible is evaporated, collecting the solid evaporated from the water, placing the solid evaporated from the water in a quartz tube of a tube furnace for calcination, and cooling and grinding after calcination. The heating temperature of the crucible is 150 DEG C. The calcination atmosphere is air, the calcination temperature is 300 DEG C, and the calcination time is 1 hour. The Al2O3 is doped with nitrogen. The phenolic compounds are phenol, 2,4-dichlorophenol, 2,4-dibromophenol, 2,4-difluorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol, pentabromophenol, nonylphenol, chlorobenzene, bisphenol A, bisphenol B, bisphenol S, benzophenone-1, benzophenone-4, or benzophenone-8.

2. The method of claim 1, wherein, Al2O3 is added to a water body containing phenolic compounds, mixed, and then KMnO4 is added to degrade the phenolic compounds, or Al2O3 and KMnO4 are mixed and then added to a water body containing phenolic compounds to degrade the phenolic compounds.

3. The method according to claim 1 or 2, characterized in that, The concentration of the phenolic compounds in the water body ranges from 2.0 μmol / L to 2.0 mmol / L.

4. The method according to claim 1 or 2, characterized in that, The KMnO4 is added in the form of an aqueous KMnO4 solution.

5. The method according to claim 1 or 2, characterized in that, The molar ratio of the phenolic compounds to KMnO4 is 1:0.5-20, the molar mass ratio of the phenolic compounds to Al2O3 is 0.01 mmol:0.1 g-2 g, the reaction temperature is 24 DEG C-26 DEG C, and the reaction time is 10-120 min.

6. The method of claim 1 or 2, wherein, The degradation reaction is carried out at a pH of 5-10.

7. The method according to claim 1 or 2, characterized in that, The degradation of the phenolic compounds is carried out in a conventional reactor or a fixed bed reactor.

8. The method of claim 7, wherein, When a fixed bed reactor is used, Al2O3 is placed in the fixed bed, and the water body penetrates the fixed bed to carry out the degradation reaction.

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