A method for promoting degradation of triphenyl phosphate by graphene oxide
By introducing graphene oxide into the photoactivated persulfate reaction, the problem of low degradation efficiency of triphenyl phosphate in the existing technology was solved, and the efficient degradation of triphenyl phosphate in water was achieved with a degradation rate of over 99%.
Patent Information
- Application Number
- CN202410440587.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-12
- Publication Date
- 2026-02-06
- Estimated Expiration
- 2044-04-12
AI Technical Summary
Existing photoactivated persulfate technology has low efficiency in degrading triphenyl phosphate in the aquatic environment, making it difficult to achieve efficient removal.
Using graphene oxide as an electron transfer medium, the degradation of triphenyl phosphate is promoted through photo-activated advanced oxidation reaction of persulfate. The specific steps include mixing graphene oxide dispersion with triphenyl phosphate aqueous solution and adding persulfate to carry out photo-reaction.
The efficient degradation of triphenyl phosphate in water was achieved, with a degradation rate of over 99% within 20 minutes. The hydrophilicity, abundant surface functional groups, and high specific surface area of graphene oxide were utilized to improve the reaction efficiency of photoactivated persulfate.
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Figure CN118084178B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of wastewater treatment technology containing organic pollutants, and specifically relates to a method for promoting the degradation of triphenyl phosphate using graphene oxide. Background technology:
[0002] Triphenyl phosphate is a typical aryl organophosphate flame retardant widely used in commercial products such as electronic devices and plastics. It is also frequently detected in various environments, including air, water, and sediments. Due to its widespread distribution and potential endocrine-disrupting effects, neurotoxicity, and developmental toxicity, triphenyl phosphate has become a prominent emerging organic pollutant, making the development of an efficient treatment method for removing it from polluted water bodies urgent and necessary.
[0003] Activation of persulfate can generate highly reactive oxygen species with strong oxidizing capabilities, such as hydroxyl radicals, superoxide anion radicals, sulfate radicals, and singlet oxygen. Therefore, this technology shows promising application prospects in the oxidative degradation and removal of trace organic pollutants in aquatic environments. Persulfate activation methods include photoactivation, thermal activation, alkali activation, and activation with metal or carbon-based catalysts. Photoactivation of persulfate has advantages such as being clean and utilizing sunlight, but its efficiency is generally low. Summary of the Invention
[0004] Based on the necessity of proper treatment of triphenyl phosphate wastewater and the low efficiency of existing photo-activated persulfate methods, this application discloses a method for promoting the degradation of triphenyl phosphate using graphene oxide. This method can achieve efficient degradation (>99%) of low concentrations of triphenyl phosphate in water.
[0005] This application is achieved through the following technical solution:
[0006] A method for promoting the degradation of triphenyl phosphate using graphene oxide includes:
[0007] A mixture was obtained by mixing an aqueous solution containing triphenyl phosphate and a graphene oxide dispersion;
[0008] Adding persulfate to the mixture causes photoreactive degradation of triphenyl phosphate.
[0009] Preferably, the average sheet diameter of the graphene oxide is 200-500 nm.
[0010] Preferably, the concentration of the triphenyl phosphate is 10 μmol / L.
[0011] Preferably, the concentration of graphene oxide in the mixture is 2-8 mg / L.
[0012] Preferably, the persulfate is a potassium persulfate compound salt, and the addition amount is 100-400 mg / L.
[0013] Preferably, the light source for the photoreaction is a 300W xenon lamp.
[0014] The beneficial effects of this invention are as follows:
[0015] This application utilizes the advantages of graphene oxide, such as its good hydrophilicity, abundant surface functional groups, large specific surface area, high stability, and strong charge transfer ability, to apply it as an electron transfer medium in the advanced oxidation reaction of photoactivated persulfate. This effectively promotes electron transfer, the generation of reactive oxygen species, and the contact between the pollutant triphenyl phosphate molecules and the catalytically active sites during the photoactivated persulfate reaction, thereby achieving the goal of efficient degradation and removal of triphenyl phosphate from water. After treatment with the technology described in this invention, the degradation rate of 10 μmol / L triphenyl phosphate in water reached over 99% within 20 minutes. Attached Figure Description
[0016] Figure 1 The experimental results show the effect of the amount of graphene oxide on the degradation efficiency of triphenyl phosphate by photoactivated persulfate.
[0017] Figure 2 The experimental results show the effect of the amount of persulfate on the degradation efficiency of triphenyl phosphate by photoactivated persulfate.
[0018] Figure 3 The results show the effect of initial solution pH on the degradation efficiency of photoactivated persulfate of triphenyl phosphate.
[0019] Figure 4 The results show the effect of the average size of graphene oxide flakes on the degradation efficiency of triphenyl phosphate by photoactivated persulfate. Detailed Implementation
[0020] The present invention will now be described in detail with reference to embodiments and accompanying drawings. However, it should be understood that the embodiments and drawings are for illustrative purposes only and do not constitute any limitation on the scope of protection of the present invention. All reasonable modifications and combinations included within the inventive spirit of the present invention fall within the scope of protection of the present invention.
[0021] The embodiments of this application disclose a method for promoting the degradation of triphenyl phosphate using graphene oxide, comprising: mixing an aqueous solution containing triphenyl phosphate and a graphene oxide dispersion to obtain a mixture; adding persulfate to the mixture; and photodegrading triphenyl phosphate.
[0022] In this embodiment, the graphene oxide dispersion is commercially available. It is understood that this dispersion can also be obtained by methods not exceeding the understanding of those skilled in the art, such as preparation by those skilled in the art. In the mixture, the concentration of the graphene oxide dispersion is 2-8 mg / L. At this concentration, the degradation and removal efficiency of triphenyl phosphate reaches over 97% after 20 minutes of reaction, particularly exceeding 99% at 4-8 mg / L. To demonstrate the above technical effects, this application discloses the following specific experimental examples.
[0023] Experiment 1: Effect of graphene oxide dosage on the degradation rate of triphenyl phosphate by photoactivated persulfate.
[0024] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (concentration 2 mmol / L), and different volumes (200, 400, 600, or 800 μL) of graphene oxide dispersion (concentration 1 mg / mL, resulting in graphene oxide dispersion concentrations of 2, 4, 6, and 8 mg / L in the mixture) were added. The pH of the mixture was approximately 6.4. The reactor was stirred at 500 rpm, and the circulating cooling water temperature was 25°C. After adding 20 mg of persulfate to the solution, a xenon lamp was turned on, and the reaction was irradiated for 20 min. Samples (0.5 mL each) were taken at time points of 0, 1, 2, 4, 6, 8, 10, 15, and 20 min. Each sample was mixed with 0.5 mL of methanol, and the graphene oxide was removed using a syringe filter. The remaining triphenyl phosphate content in the clarified filtrate was detected using high-performance liquid chromatography (HPLC), and the degradation and removal efficiency of triphenyl phosphate was calculated.
[0025] Experimental results are as follows Figure 1 (Experimental results on the effect of graphene oxide dosage on the degradation efficiency of photoactivated persulfate of triphenyl phosphate) show that after 20 min of reaction, the removal rate of triphenyl phosphate was 72.5% without the use of graphene oxide; the addition of 2 mg / L graphene oxide greatly promoted the degradation and removal of triphenyl phosphate, and the removal rate was 97.2% after 20 min of reaction; while when using 4, 6 or 8 mg / L graphene oxide, the degradation and removal efficiency of triphenyl phosphate reached more than 99% after 20 min of reaction.
[0026] In this embodiment, the reaction instrument is preferably a glass-jacketed photoreactor, which can achieve the purpose of stirring the mixture after mixing in the glass-jacketed photoreactor to obtain a uniform mixture. In this application, the stirring speed is preferably 500 rpm. At the same time, the reaction temperature can be controlled by circulating cooling water during the photoreaction. In this embodiment, the specific reaction temperature is controlled at 25°C for the temperature of the circulating cooling water. However, it is understood that those skilled in the art can also achieve the purpose of stirring the mixture and controlling the reaction temperature in other ways.
[0027] In some preferred embodiments, the persulfate is a potassium persulfate complex salt, added in solid form at an amount of 100-400 mg / L. At this concentration, the degradation and removal efficiency of triphenyl phosphate is highest. To demonstrate the above technical effects, this application discloses the following specific experimental examples.
[0028] Experimental Example 2: Effect of Persulfate Dosage on the Degradation Rate of Triphenyl Phosphate by Photoactivated Persulfate.
[0029] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (concentration 2 mmol / L), and 400 μL of graphene oxide dispersion (concentration 1 mg / mL, making the graphene oxide dispersion concentration in the mixture 4 mg / L) were added. At this point, the pH of the mixture was approximately 6.4. The reactor stirring speed was set to 500 rpm, and the circulating cooling water temperature was set to 25°C. 10, 20, 30, or 40 mg of permonosulfate were added to the above solution (making the permonosulfate concentrations in the mixture 100, 200, 300, and 400 mg / L, respectively). The xenon lamp was turned on, and the reaction was irradiated for 20 min. Samples were taken at time points of 0, 1, 2, 4, 6, 8, 10, 15, and 20 min, with 0.5 mL of sample taken each time. After mixing with 0.5 mL of methanol, the graphene oxide was filtered out using a syringe filter. The content of residual triphenyl phosphate in the clarified filtrate was detected by high performance liquid chromatography, and the efficiency of triphenyl phosphate degradation and removal was calculated.
[0030] Experimental results are as follows Figure 2 (Experimental results on the effect of persulfate dosage on the degradation efficiency of triphenyl phosphate by photoactivated persulfate) show that after 20 min of reaction, the degradation and removal efficiency of triphenyl phosphate reached over 99% under the conditions of persulfate concentration of 100-400 mg / L.
[0031] In some preferred embodiments, the pH of the mixture is adjusted to 6.4. In actual treatment of water containing triphenyl phosphate, the presence of other components in the wastewater can affect the pH of the water. This embodiment found that the closer the pH is to the actual pH (6.4) of the triphenyl phosphate solution, the more significant the degradation efficiency. To demonstrate the above technical effects, this application discloses the following specific experimental examples.
[0032] Experimental Example 3: Effect of initial solution pH on the degradation efficiency of photoactivated persulfate-degraded triphenyl phosphate.
[0033] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (concentration 2 mmol / L), and 400 μL of graphene oxide dispersion (concentration 1 mg / mL, making the graphene oxide dispersion concentration in the mixture 4 mg / L) were added. The pH of the above solution was adjusted to 3, 5, 7, 9, or 11 with HCl or NaOH. The stirring speed of the reactor was set to 500 rpm, and the circulating cooling water temperature was set to 25℃. After adding 20 mg of permonosulfate to the above solution (making the permonosulfate concentration in the mixture 200 mg / L), the xenon lamp source was turned on, and the reaction was irradiated for 20 min. Samples were taken at time points of 0, 1, 2, 4, 6, 8, 10, 15, and 20 min of the reaction, with 0.5 mL of sample taken each time. After mixing with 0.5 mL of methanol, the graphene oxide was filtered out using a syringe filter. The content of residual triphenyl phosphate in the clarified filtrate was detected by high performance liquid chromatography, and the efficiency of triphenyl phosphate degradation and removal was calculated.
[0034] Experimental results are as follows Figure 3 As shown, the degradation efficiency of triphenyl phosphate varies under different initial solution pH conditions. The highest degradation efficiency is observed under near-neutral conditions. For example, after 20 minutes of reaction, the removal efficiency of triphenyl phosphate reaches 98.2% (pH=7). According to Experiments 1 and 2, the removal efficiency is highest (over 99%) in natural water at pH 6.4. This demonstrates that the closer the pH is to the actual pH of the triphenyl phosphate solution, the more significant the degradation effect. Therefore, in practical operations, pH adjusters such as hydrochloric acid or sodium hydroxide can be used to adjust the water pH to 6.4. Excessively acidic or alkaline pH conditions are unfavorable for the degradation and removal of triphenyl phosphate, but even at these conditions, more than 50% of the triphenyl phosphate can still be removed after 20 minutes of reaction.
[0035] In some preferred embodiments, the light source for the photoreaction is a 300W xenon lamp.
[0036] In some preferred embodiments, the average diameter of the graphene oxide is 200nm-500nm, which is the size at which the removal efficiency of triphenyl phosphate is the best. To demonstrate the above technical effect, this application discloses the following specific test examples.
[0037] Experiment 4: Effect of the average size of graphene oxide flakes on the degradation efficiency of photoactivated persulfate-degraded triphenyl phosphate.
[0038] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (concentration 2 mmol / L), and 400 μL of graphene oxide dispersion with an average sheet diameter of 200 nm or 500 nm (concentration 1 mg / mL) were added. The circulating cooling water temperature was 25 °C. After adding 20 mg of persulfate to the above solution, the xenon lamp was turned on, and the reaction was irradiated for 20 min. Samples (0.5 mL each) were taken at time points 2, 4, 6, 10, 15, and 20 min of the reaction. The sample was mixed with 0.5 mL of methanol and filtered through a syringe filter to remove the graphene oxide. The residual triphenyl phosphate content in the clarified filtrate was detected using high-performance liquid chromatography (HPLC), and the degradation and removal efficiency of triphenyl phosphate was calculated. Figure 4 As shown, the size of graphene oxide sheets has no significant effect on the degradation and removal efficiency of triphenyl phosphate. Using graphene oxide with an average sheet size of 200 nm or 500 nm, more than 99% of triphenyl phosphate can be removed after 20 min of reaction.
[0039] In some preferred embodiments, the concentration of triphenyl phosphate in the aqueous solution containing triphenyl phosphate is 10 μmol / L. After the addition of graphene oxide, persulfate has the highest degradation rate of triphenyl phosphate at this concentration, reaching more than 99% within 20 minutes.
[0040] Example 1: A method for promoting the degradation of triphenyl phosphate using graphene oxide
[0041] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (2 mmol / L), and 400 μL of graphene oxide dispersion with an average sheet diameter of 200 nm (1 mg / mL) were added. At this point, the pH of the mixture was approximately 6.4, and the circulating cooling water temperature was 25 °C. After adding 20 mg of persulfate to the above solution, the xenon lamp was turned on, and the reaction was irradiated for 20 min.
[0042] Example 2: A method for promoting the degradation of triphenyl phosphate using graphene oxide
[0043] In a glass-jacketed photoreactor, 100 mL of water, 500 μL of triphenyl phosphate solution (2 mmol / L), and 800 μL of graphene oxide dispersion with an average sheet diameter of 500 nm (1 mg / mL) were added. At this point, the pH of the mixture was approximately 6.4, and the circulating cooling water temperature was 25 °C. After adding 40 mg of persulfate to the above solution, the xenon lamp was turned on, and the reaction was irradiated for 20 min.
[0044] Example 3: A method for promoting the degradation of triphenyl phosphate using graphene oxide
[0045] In a glass-jacketed photoreactor, add 100 mL of water, 500 μL of triphenyl phosphate solution (concentration 2 mmol / L), and 200 μL of graphene oxide dispersion with an average sheet diameter of 200 nm (concentration 1 mg / mL), adjust the pH to 7, and maintain the circulating cooling water temperature at 25 °C. Add 10 mg of persulfate to the above solution, then turn on the xenon lamp and irradiate the reaction for 20 min.
[0046] The embodiments described above are some, but not all, of the embodiments of this application. The detailed description of the embodiments of this application is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.
Claims
1. A method for promoting the degradation of triphenyl phosphate using graphene oxide, characterized by, The application relates to a method for degrading phosphorus-containing organic pollutants in water bodies. The method comprises the following steps: mixing a water body containing triphenyl phosphate and a graphene oxide dispersion solution to obtain a mixture; adding a persulfate to the mixture, and performing photoreaction to degrade the triphenyl phosphate; the concentration of the graphene oxide in the mixture is 2-8 mg / L; the persulfate is potassium hydrogen peroxymonosulfate, and the adding amount is 100-400 mg / L; 2. The method of claim 1, wherein, the light source of the photoreaction is a 300 W xenon lamp.
3. The method of claim 1, wherein, The average flake diameter of the graphene oxide is 200-500 nm. The concentration of the triphenyl phosphate is 10 mu mol / L.