Method for treating ribavirin and chloroquine phosphate in water through ultraviolet light catalysis

The UV/KMnO4/TiO2 process coordinated removal of ribavirin and chloroquine phosphate in water solved the problem of low removal efficiency in traditional methods and achieved efficient and easy drug removal effect.

CN120383377AActive Publication Date: 2025-07-29SHANDONG WATER & WASTEWATER MONITORING CENT
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Patent Information

Application Number
CN202510545816.0
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-04-28
Publication Date
2025-07-29
Estimated Expiration
2045-04-28

AI Technical Summary

Technical Problem

Traditional sewage treatment methods are less efficient in removing ribavirin and chloroquine phosphate, resulting in enrichment of these antiviral drugs in the aqueous environment, toxicity and posing a threat to the ecosystem.

Method used

UV/KMnO4/TiO2 process was adopted, TiO2 and KMnO4 were added to water and treated under ultraviolet irradiation. Ribavirin and chloroquine phosphate were synergistically removed by photocatalytic action of TiO2 and oxidation of KMnO4.

Benefits of technology

The efficient removal of ribavirin and chloroquine phosphate is achieved, with a removal rate much higher than that of the method of using UV, UV/KMnO4 or UV/TiO2 alone. It is simple to operate and easy to obtain chemical reagents, which are suitable for engineering practice.

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Abstract

The invention provides a method for treating ribavirin and chloroquine phosphate in water through ultraviolet light catalysis, aiming at the problem of low removal efficiency of two common antiviral drugs, namely ribavirin and chloroquine phosphate, of a traditional sewage treatment method. According to the method, a certain amount of TiO2 and KMnO4 are added into water, ribavirin and chloroquine phosphate are removed under ultraviolet irradiation, the result shows that ribavirin and chloroquine phosphate can be efficiently removed through the UV / KMnO4 / TiO2 technology, the treatment effect is far better than that of methods such as independent UV, UV / KMnO4 and UV / TiO2, and the UV / KMnO4 / TiO2 technology has an obvious synergistic effect. Besides, TiO2 is the most common photocatalytic material at present, and potassium permanganate KMnO4 is a common oxidant, so that the UV / KMnO4 / TiO2 method has the characteristics of simplicity, easiness in obtaining and easiness in implementation, and can be widely applied to engineering practice.
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Description

Technical Field

[0001] The present invention belongs to the fields of environmental protection and water treatment methods, and relates to a method for photocatalytically treating ribavirin and chloroquine phosphate in water with ultraviolet light. Background Art

[0002] Ribavirin (RBV) is a common antiviral drug with in vitro activity against a variety of viruses, especially for patients with hepatitis C, and has broad-spectrum activity against many RNA and DNA viruses. It can be used to treat various types of viral infections and exhibits anti-tumor activity in colorectal cancer and hepatocellular carcinoma. Due to the continuous enrichment of RBV in water bodies and the environment, it has recently been considered a newly emerging pollutant in the environment. At present, the presence of RBV has been detected in urban sewage, surface water, groundwater and sediments. Chloroquine phosphate (CQP) is not only an antiviral drug for treating coronavirus disease, but also an old drug for treating malaria, rheumatoid arthritis and asthma. Traditional sewage treatment methods have low removal efficiency for it. Untreated or incompletely treated RBV, CQP and metabolites will be discharged into the aquatic system with the tail water. As they continuously accumulate in the water environment, they will produce certain toxicity to microorganisms such as algae and fish in the water environment, and even pose a serious threat to humans and the ecosystem. Therefore, how to effectively remove antiviral drugs represented by ribavirin is an important problem to be solved in the water treatment process.

[0003] As a deep treatment process, the ultraviolet photocatalytic oxidation method not only has a good removal effect on conventional pollutants in water, but also can treat refractory organic compounds and micropollutants that are difficult to remove by conventional treatment processes. Among them, TiO2 is the most common photocatalytic material at present, which has the advantages of strong chemical stability, low cost, non-toxicity and long service life. However, due to the relatively large band gap of TiO2 (E g = 3.2 eV), when the excitation energy is insufficient, the generated h + and e - are easily recombined again, thus reducing the catalytic efficiency. In order to increase the catalytic efficiency, in addition to the commonly used TiO2 modification, there are also treatment methods combined with other oxidation agents, such as UV / TiO2 / In2O3, UV / TiO2 / periodate (IO4-), UV / TiO2 / H2O2, etc. These methods have played a good synergistic role in the degradation of pollutants. Potassium permanganate KMnO4, as a common agent, is currently commonly used in the pretreatment and deep treatment links of water plants. However, so far, there is no report on the UV / TiO2 / KMnO4 treatment method. Summary of the Invention

[0004] In view of the above problems, the present invention provides a method for photocatalytic treatment of ribavirin and chloroquine phosphate in water by ultraviolet light. By adding a certain amount of TiO2 and KMnO4 into water and removing ribavirin and chloroquine phosphate under ultraviolet irradiation, the results show that the UV / KMnO4 / TiO2 process can efficiently remove ribavirin and chloroquine phosphate, and the treatment effect is far greater than that of methods such as single UV, UV / KMnO4, and UV / TiO2 alone, that is, the UV / KMnO4 / TiO2 process has an obvious synergistic effect. In addition, since TiO2 is the most common photocatalytic material at present and potassium permanganate KMnO4 is a common oxidant, the UV / KMnO4 / TiO2 method has the characteristics of being simple and easy to obtain and easy to implement, and can be widely applied to engineering practice.

[0005] To achieve the above object, the solution adopted by the present invention is: a method for photocatalytic treatment of ribavirin and chloroquine phosphate in water by ultraviolet light, which is characterized in that the UV / KMnO4 / TiO2 process is adopted, that is, a certain amount of TiO2 and KMnO4 are added into water containing ribavirin and / or chloroquine phosphate, and ribavirin and / or chloroquine phosphate are removed under ultraviolet irradiation.

[0006] Further, in the UV / KMnO4 / TiO2 process, the optimal conditions are: the UV light intensity is 56.5 - 206 μw / cm 2 , the TiO2 concentration is 40 - 100 mg / L, the KMnO4 concentration is 0.02 - 0.2 mM, and the pH is adjusted to 6.5 - 7.5 by using phosphate buffer solution (PBS). Further, when the UV light intensity is 206 μw / cm 2 , the TiO2 concentration is 80 mg / L, the KMnO4 concentration is 0.02 mM, and the degradation effect is the best under the condition of pH = 7.00.

[0007] In the present invention, the UV / KMnO4 / TiO2 process acts simultaneously to generate strong degradation groups for efficiently removing ribavirin and chloroquine phosphate, mainly including strong oxidizing metals such as Mn(Ⅶ), Mn(V), Mn(Ⅲ) and free radicals h + , OH·, etc.

[0008] Further, the experimental device adopted by the present invention is a parallel beam instrument, the lamp tube is an ultraviolet low-pressure mercury lamp (power 70W), the emission wavelength is 254 nm, and the light beam directly irradiates the reaction solution below through a circular tube. A reaction dish with a volume of 200 mL is selected and placed at a fixed position during each test, and the ultraviolet dose is accurately measured by a light intensity meter. The common ultraviolet dose is 206 μW / cm 2 .

[0009] The present invention has the following characteristics:

[0010] 1) When t = 45 min in the present invention, the removal effect on RBV can reach more than 86%, which can effectively reduce the further accumulation of RBV in water.

[0011] 2) When t = 5 min in the present invention, the removal effect on chloroquine phosphate can reach more than 91%, which can effectively reduce the further accumulation of ribavirin in water.

[0012] 3) For the removal of ribavirin and chloroquine phosphate, the treatment effect is much greater than that of methods such as single UV, UV / KMnO4, and UV / TiO2, that is, the UV / KMnO4 / TiO2 process has an obvious synergistic effect. For the removal of RBV, the pseudo-first-order degradation rate constant of UV / TiO2 / KMnO4 is 0.0426 min -1 >>0.0233 min -1 (the pseudo-first-order degradation rate constant of UV / TiO2)+0.002 min -1 (the pseudo-first-order degradation rate constant of UV / KMnO4); for the removal of CQP, the pseudo-first-order degradation rate constant of UV / TiO2 / KMnO4 is 0.473 min-1>>0.1919 min-1 (the pseudo-first-order degradation rate constant of UV / TiO2)+0.0032 min -1 (the pseudo-first-order degradation rate constant of UV / KMnO4).

[0013] The present invention has good safety, simple operation, and the reaction environment is easy to achieve. The chemical reagents added are common products in water treatment, so the feasibility and operability are relatively strong, and it is also relatively easy to promote and implement in reality. Description of the Drawings

[0014] Figure 1 It is a schematic diagram of the reaction device;

[0015] Figure 2 It is the experimental result of the degradation of RBV by the UV / KMnO4 / TiO2 process under three kinds of quenchers; among them, Figure (a) is the C / CO result, and Figure (b) is the -ln(C / CO) result;

[0016] Figure 3 It is the experimental result of the degradation of RBV by the UV / KMnO4 / TiO2 process at different KMnO4 concentrations; among them, Figure (a) is the C / CO result, Figure (b) is the -ln(C / CO) result; Figure (c) is the test result of the RBV removal rate;

[0017] Figure 4Degradation experiment results of RBV by the UV / KMnO4 / TiO2 process at different TiO2 concentrations; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results; (c) shows the RBV removal rate test results;

[0018] Figure 5 Degradation experiment results of RBV by the UV / KMnO4 / TiO2 process at different ultraviolet light intensities; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results;

[0019] Figure 6 Comparison of degradation experiment results of RBV by UV / KMnO4 / TiO2 with UV alone, UV / KMnO4, and UV / TiO2; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results; (c) shows the RBV removal rate test results;

[0020] Figure 7 Degradation experiment results of CQP by the UV / KMnO4 / TiO2 process with three quenchers; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results;

[0021] Figure 8 Degradation experiment results of CQP by the UV / KMnO4 process at different KMnO4 concentrations; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results;

[0022] Figure 9 Degradation experiment results of CQP by the UV / KMnO4 / TiO2 process at different KMnO4 concentrations; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results; (c) shows the CQP removal rate test results;

[0023] Figure 10 Degradation experiment results of CQP by the UV / KMnO4 / TiO2 process at different TiO2 concentrations; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results; (c) shows the CQP removal rate test results;

[0024] Figure 11 Degradation experiment results of CQP by the UV / KMnO4 / TiO2 process at different ultraviolet light intensities; among them, (a) shows the C / CO results, (b) shows the -ln(C / CO) results;

[0025] Figure 12 Comparison of degradation experiment results of CQP by UV / KMnO4 / TiO2 with UV alone, UV / KMnO4, and UV / TiO2. Detailed implementation method

[0026] The effects will be described below in conjunction with embodiments and the accompanying drawings.

[0027] Figure 1 As shown in the schematic diagram of the reaction device, Figure 1 the ultraviolet experimental device of the present invention includes an ultraviolet lamp tube, a movable bracket, a magnetic stirrer, a rotor, etc. Among them, the ultraviolet lamp tube is connected to a power source through a power connection line to generate ultraviolet light.

[0028] The experimental device adopted in the present invention is a parallel beam instrument. The lamp tube is an ultraviolet low-pressure mercury lamp (power 70W), and the emission wavelength is 254nm. The light beam directly irradiates the reaction solution below through a circular tube. A reaction dish with a volume of 200 mL is selected and placed at a fixed position during each test. The ultraviolet dose is accurately measured by a light intensity meter, and the commonly used ultraviolet dose is 206 μW / cm 2 .

[0029] Example 1: Experimental study on the degradation of ribavirin (RBV) by the UV / KMnO4 / TiO2 process

[0030] 1. Radical identification

[0031] Use ultrapure water to prepare the initial concentration of RBV to be 2.5 μM, and conduct degradation experiments on RBV by the UV / KMnO4 / TiO2 process under three kinds of quenchers respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating RBV is: [UV light intensity] = 206 μw / cm 2 , [ribavirin] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L, and use phosphate buffer solution (PBS) to adjust pH = 7.00, and the concentration of phosphate buffer solution is 5 mM.

[0032] The results are as Figure 2 shown. In the water containing RBV, an excessive amount of tert-butanol (TBA) is added respectively to quench OH·, an excessive amount of PSMO (methylphenyl sulfoxide) to quench Mn(V) and OH·, and an excessive amount of ammonium oxalate (AO) to quench holes (h + +), and the results prove that: hydroxyl radical (OH·) is the main substance directly reacting with RBV, accounting for about 85%.

[0033] 2. Influence of different KMnO4 concentrations on the reaction

[0034] Use ultrapure water to prepare the initial concentration of RBV to be 2.5 μM, and conduct degradation experiments on RBV under different KMnO4 concentrations respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating RBV is: [UV light intensity] = 206 μw / cm 2, [Ribavirin] = 2.5 μM, [KMnO4] = 0 - 0.2 mM, [TiO2] = 80 mg / L, adjust the pH = 7.00 using phosphate buffer solution, and the concentration of phosphate buffer solution is 5 mM.

[0035] As Figure 3 shown, in water containing RBV, fix the dosage of TiO2 at 80 mg / L, and the dosages of KMnO4 are 0 mM, 0.01 mM, 0.02 mM, 0.05 mM, 0.1 mM, and 0.2 mM respectively. The results prove that when the dosage of KMnO4 is 0.02 mM, the removal rate can reach up to 86% at the reaction time t = 45 min, and the reaction rate constant K obs = 0.0426. Compared with the case without adding KMnO4, the removal rate can be increased by 20%. When the dosage of KMnO4 is 0.05 mM, the removal rate of RBV can reach up to 91%, and the reaction rate constant K obs = 0.0531.

[0036] 3. Influence of different TiO2 concentrations on the reaction

[0037] Prepare the initial concentration of RBV as 2.5 μM with ultrapure water, and conduct the degradation experiments of RBV at different TiO2 concentrations respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating RBV is: [UV intensity] = 206 μw / cm 2 , [Ribavirin] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 0 - 100 mg / L, adjust the pH = 7.00 using phosphate buffer solution, and the concentration of phosphate buffer solution is 5 mM.

[0038] The results are as Figure 4 shown. In water containing RBV, fix the dosage of KMnO4 at 0.02 mM, and the dosages of TiO2 are 0 mg / L, 20 mg / L, 40 mg / L, 60 mg / L, 80 mg / L, and 100 mg / L respectively. The results prove that when the dosage of TiO2 is 80 mg / L, the removal rate can reach up to 86% at the reaction time t = 45 min, and the reaction rate constant K obs = 0.0426. Compared with the case without adding TiO2, the removal rate can be increased by 77%.

[0039] 4. Influence of different ultraviolet light intensities

[0040] Prepare an initial concentration of 2.5 μM of RBV with ultrapure water and conduct degradation experiments of RBV under different UV light intensities respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating RBV is as follows: [Ribavirin] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L. Adjust the pH to 7.00 using phosphate buffer solution, the phosphate buffer solution is 5 mM, and adjust [UV light intensity] = 56.5 - 206 μW / cm 2 。

[0041] The results are as Figure 5 shown. In the water containing RBV, fix the dosage of KMnO4 at 0.02 mM, the dosage of TiO2 at 80 mg / L respectively, and adjust the UV light intensity [UV light intensity] = 56.5, 103, 206 μW / cm 2 , and the results prove that when the UV light intensity is 56.5 μW / cm 2 , the removal rate is 47%, and the reaction rate constant K obs = 0.0133; when the UV light intensity is 206 μW / cm 2 , the removal rate is 86% at the reaction time t = 45 min, and the reaction rate constant K obs = 0.0426.

[0042] 5. Comparison of the UV / KMnO4 / TiO2 process with UV alone, UV / KMnO4, and UV / TiO2

[0043] Prepare an initial concentration of 2.5 μM of RBV with ultrapure water and conduct degradation experiments of RBV under four processes (UV / KMnO4 / TiO2, UV, UV / KMnO4, UV / TiO2) respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating RBV is as follows: [Ribavirin] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L. Adjust the pH to 7.00 using phosphate buffer solution, the phosphate buffer solution is 5 mM, and adjust [UV light intensity] = 206 μW / cm 2 . Remove the corresponding test conditions for the UV, UV / KMnO4, and UV / TiO2 processes respectively, and the rest is the same as the UV / KMnO4 / TiO2 process.

[0044] Table 1 Treatment effects of different combined UV advanced oxidation processes on RBV

[0045] RBV Removal Process <![CDATA[k obs min -1 > Multiplier K <![CDATA[UV / TiO2 / KMnO4]]> 0.0426 1.00 <![CDATA[UV / TiO2]]> 0.0233 0.55 <![CDATA[UV / KMnO4]]> 0.002 0.05 UV 0.0015 0.04

[0046] As shown in Table 1 and Figure 6 shown: For the removal of RBV, the pseudo-first-order rate constant of degradation of UV / TiO2 / KMnO4 is 0.0426 min -1>>0.0233 min -1 (Pseudo-first-order degradation rate constant of UV / TiO2) + 0.002 min -1 (Pseudo-first-order degradation rate constant of UV / KMnO4). Therefore, UV / TiO2 / KMnO4 has a better synergistic promotion effect than both UV / TiO2 and UV / KMnO4.

[0047] Example 2: Experimental study on the degradation of chloroquine phosphate (CQP) by the UV / KMnO4 / TiO2 process

[0048] 1. Radical identification

[0049] Prepare an initial concentration of CQP of 2.5 μM with ultrapure water, and conduct degradation experiments of CQP by the UV / KMnO4 / TiO2 process under three kinds of quenchers respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating CQP is: [UV light intensity] = 206 μw / cm 2 , [chloroquine phosphate] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L, adjust the pH = 7.00 with phosphate buffer solution, and the concentration of phosphate buffer solution is 5 mM.

[0050] The results are as Figure 7 shown. In the water containing CQP, add excessive tert-butanol (TBA) and isopropanol (IPA) to quench OH·, excessive PSMO to quench Mn(V) and OH·, and excessive ammonium oxalate (AO) to quench holes (h + ). The results prove that: holes (h + ) are the main substances directly reacting with CQP, accounting for about 61.82%.

[0051] 2. Influence of different KMnO4 concentrations on the reaction under the UV / KMnO4 process

[0052] Prepare an initial concentration of CQP of 2.5 μM with ultrapure water, and conduct degradation experiments of CQP under different KMnO4 concentrations respectively. The experimental operation of the UV / KMnO4 process for treating CQP is: [UV light intensity] = 206 μw / cm 2 , [chloroquine phosphate] = 2.5 μM,

[0053] [KMnO4] = 0 - 0.2 mM, adjust the pH = 7.00 with phosphate buffer solution, and the concentration of phosphate buffer solution is 5 mM.

[0054] As follows Figure 8As shown, in the water containing CQP, the dosage of TiO2 is 0 mg / L, and the dosages of KMnO4 are 0 mM, 0.02 mM, 0.05 mM, 0.1 mM, and 0.2 mM respectively. The results show that when the dosage of KMnO4 is 0.02 mM, the removal rate is only 18%, and the reaction rate constant K obs = 0.0032. When the dosage of KMnO4 is 0.20 mM, the removal rate of CQP is about 60% at the reaction time t = 60 min, and the reaction rate constant K obs = 0.0136.

[0055] 3. Influence of Different KMnO4 Concentrations on the Reaction under the UV / KMnO4 / TiO2 Process

[0056] The initial concentration of CQP was configured to be 2.5 μM with ultrapure water, and the degradation experiments of CQP were carried out at different KMnO4 concentrations. The experimental operation of treating CQP by the UV / KMnO4 / TiO2 process was: [UV light intensity] = 206 μw / cm 2 , [chloroquine phosphate] = 2.5 μM, [KMnO4] = 0 - 0.2 mM, [TiO2] = 80 mg / L, and the pH was adjusted to 7.00 with phosphate buffer solution, and the concentration of phosphate buffer solution was 5 mM.

[0057] The results are as Figure 9 shown. In the water containing CQP, with the dosage of TiO2 fixed at 80 mg / L, the dosages of KMnO4 are 0 mM, 0.01 mM, 0.02 mM, 0.04 mM, 0.08 mM, 0.1 mM, and 0.2 mM respectively. The results show that when the dosage of KMnO4 is 0.02 mM, the removal rate can reach up to 91% at the reaction time t = 5 min, and the reaction rate constant K obs = 0.473. Compared with the case without adding KMnO4, the removal rate can be increased by 25%. When the dosage of KMnO4 is 0.20 mM, the highest removal rate of CQP can reach 98%, and the reaction rate constant K obs = 0.7636.

[0058] 4. Influence of Different TiO2 Concentrations on the Reaction

[0059] The initial concentration of CQP was configured to be 2.5 μM with ultrapure water, and the degradation experiments of CQP were carried out at different TiO2 concentrations. The experimental operation of treating CQP by the UV / KMnO4 / TiO2 process was: [UV light intensity] = 206 μw / cm 2 , [chloroquine phosphate] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 0 - 100 mg / L, and the pH was adjusted to 7.00 with phosphate buffer solution, and the concentration of phosphate buffer solution was 5 mM.

[0060] The results are as Figure 10 shown. The dosage of KMnO4 was fixed at 0.02 mM, and the dosages of TiO2 were 0 mg / L, 20 mg / L, 40 mg / L, 60 mg / L, 80 mg / L, and 100 mg / L respectively. The results showed that when the dosage of TiO2 was 80 mg / L, the removal rate reached up to 91% at the reaction time t = 5 min, and the reaction rate constant K obs = 0.473. Compared with the case without adding TiO2, the removal rate could be increased by 73%.

[0061] 5. Influence of different UV light intensities

[0062] The initial concentration of CQP was configured to be 2.5 μM with ultrapure water, and the degradation experiments of CQP were carried out under different UV light intensities respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating CQP was: [chloroquine phosphate] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L. The pH was adjusted to 7.00 with phosphate buffer solution, and the concentration of phosphate buffer solution was 5 mM. The [UV light intensity] was adjusted to 56.5 - 206 μw / cm 2 .

[0063] As Figure 11 shown, in the water containing CQP, the dosage of KMnO4 was fixed at 0.02 mM, the dosage of TiO2 was 80 mg / L, and the UV light intensity [UV light intensity] was adjusted to 56.5, 103, and 206 μw / cm 2 . The results showed that: when the UV light intensity was 56.5 μw / cm 2 , the removal rate was about 53%, and the reaction rate constant K obs = 0.154; when the UV light intensity was 206 μw / cm 2 , the removal rate was 91% at the reaction time t = 5 min, and the reaction rate constant K obs = 0.473.

[0064] 6. Comparison of the UV / KMnO4 / TiO2 process with UV alone, UV / KMnO4, and UV / TiO2

[0065] The initial concentration of CQP was configured to be 2.5 μM with ultrapure water, and the degradation experiments of CQP were carried out under four processes (UV / KMnO4 / TiO2, UV, UV / KMnO4, UV / TiO2) respectively. The experimental operation of the UV / KMnO4 / TiO2 process for treating CQP was: [UV light intensity] = 206 μw / cm 2, [chloroquine phosphate] = 2.5 μM, [KMnO4] = 0.02 mM, [TiO2] = 80 mg / L, and the pH was adjusted to 7.00 using phosphate buffer with a concentration of 5 mM. The UV, UV / KMnO4, and UV / TiO2 processes removed the corresponding test conditions, and the rest was the same as the UV / KMnO4 / TiO2 process.

[0066] Table 2 Treatment effects of different combinations of ultraviolet advanced oxidation processes on CQP

[0067] CQP Processing Process <![CDATA[k obs min -1 > Multiplier K <![CDATA[UV / TiO2 / KMnO4]]> 0.473 1.00 <![CDATA[UV / TiO2]]> 0.1919 0.41 <![CDATA[UV / KMnO4]]> 0.0032 0.01 UV 0.0022 0.007

[0068] As shown in Table 2 and Figure 12 it can be seen that for the removal of CQP, the pseudo-first-order degradation rate constant of UV / TiO2 / KMnO4 was 0.473 min -1 >> 0.1919 min -1 (the pseudo-first-order degradation rate constant of UV / TiO2) + 0.0032 min -1 (the pseudo-first-order degradation rate constant of UV / KMnO4). Therefore, UV / TiO2 / KMnO4 has a good synergistic promotion effect compared with both UV / TiO2 and UV / KMnO4.

Claims

1. A method for photocatalytic treatment of ribavirin and chloroquine phosphate in water by ultraviolet light, characterized in that, The UV / KMnO4 / TiO2 process is adopted, specifically: a certain amount of TiO2 and KMnO4 are added to the water containing ribavirin and / or chloroquine phosphate, and ribavirin and / or chloroquine phosphate are removed under ultraviolet irradiation.

2. The method for photocatalytic treatment of ribavirin and chloroquine phosphate in water as described in claim 1, characterized in that UV The / KMnO4 / TiO2 process acts simultaneously to generate strong degradation groups that can efficiently remove ribavirin and chloroquine phosphate.

3. The method for photocatalytic treatment of ribavirin and chloroquine phosphate in water according to claim 2, characterized in that, The strong degradation groups include strong oxidizing metals including Mn(Ⅶ), Mn(V), Mn(Ⅲ) and free radicals h + , OH·.

4. The method for photocatalytically treating ribavirin and chloroquine phosphate in water as described in claim 1, characterized in that UV In the / KMnO4 / TiO2 process, the UV light intensity is 56.5 - 206 μw / cm 2 , the TiO2 concentration is 40 - 100 mg / L, the KMnO4 concentration is 0.02 - 0.2 mM, and the pH is adjusted to 6.5 - 7.

5.

5. The method for photocatalytic treatment of ribavirin and chloroquine phosphate in water as described in claim 4, characterized in that UV In the / KMnO4 / TiO2 process, the UV light intensity is 206 μw / cm 2 , the TiO2 concentration is 80 mg / L, the KMnO4 concentration is 0.02 mM, and pH = 7.

00.

6. A method for photocatalytically treating ribavirin and chloroquine phosphate in water with ultraviolet light according to any one of claims 1-5, characterized in that, A parallel beam instrument is used, and the lamp tube is an ultraviolet low-pressure mercury lamp with an emission wavelength of 254 nm. The light beam directly irradiates the reaction solution below through a circular tube.

7. The method for photocatalytically treating ribavirin and chloroquine phosphate in water according to claim 6, characterized in that, During each experiment, it is placed at a fixed position, and the ultraviolet dose is accurately measured by a light intensity meter.

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