Alkaline enhanced copper-based material activated peroxy monosulfate water treatment method and device

Abstract

The application provides a kind of alkali reinforced copper-based material excitation peroxymonosulfate water treatment method and device, it is related to wastewater treatment technical field, the method includes: adding alkali agent, copper-based material, peroxymonosulfate into water to be treated;The alkali agent is sodium hydroxide and / or potassium hydroxide;The copper-based material is copper oxide and / or copper sulfide.The application has the advantages of excellent pollutant treatment effect, mild reaction condition, simple process flow, green environmental protection, energy saving, easy recovery and recycling, etc., realizes the purpose of small dosage of oxidizing agent and catalyst, high utilization rate of oxidizing agent, small amount of metal ion dissolution and pH of effluent reaching standard.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to a method and apparatus for treating peroxymonosulfate using alkali-enhanced copper-based materials. Background Technology

[0002] In recent years, a new class of pollutants, distinct from traditional recalcitrant organic pollutants, has gradually emerged. This class of pollutants mainly encompasses four typical categories: persistent organic pollutants, endocrine disruptors, antibiotics and resistance genes, and microplastics. They are characterized by strong bioaccumulation, significant environmental persistence, and complex ecotoxicity.

[0003] Advanced oxidation technologies based on peroxymonosulfate (PFOS) offer core advantages such as low-cost oxidants and safe and stable storage and transportation. However, they generally suffer from technical bottlenecks, including complex preparation processes for high-efficiency catalysts, excessive dosage of oxidants and catalysts, low oxidant utilization, metal ion leaching, and excessive acidity in the effluent, which limit their engineering applications. Existing water treatment technologies exhibit numerous technical deficiencies in addressing these new pollutants, necessitating the development of innovative water treatment technology systems with high-efficiency removal capabilities to meet the urgent needs of environmental governance. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] In view of this, the present invention provides an alkali-enhanced copper-based material-activated peroxymonosulfate treatment method and apparatus to solve technical problems such as excessive dosage of oxidant and catalyst, low oxidant utilization, metal ion leaching, and excessive acidity of effluent in the peroxymonosulfate treatment system.

[0006] (II) Technical Solution

[0007] The technical solution of this invention is implemented as follows:

[0008] One aspect of this disclosure provides a method for treating peroxymonosulfate water by alkali-enhanced copper-based materials, the method comprising: adding an alkali agent, a copper-based material, and peroxymonosulfate to the water to be treated for reaction.

[0009] The alkaline agent is sodium hydroxide and / or potassium hydroxide.

[0010] The copper-based material is copper oxide and / or copper sulfide.

[0011] According to one embodiment of the present invention, the peroxymonosulfate is one or a combination of two or more of potassium peroxymonosulfate, sodium peroxymonosulfate, and calcium peroxymonosulfate.

[0012] According to one embodiment of the present invention, the alkali and peroxymonosulfate are added in solution form, wherein the molar ratio of hydroxide ions to peroxymonosulfate is 0.5 to 2.5:1.

[0013] According to one embodiment of the present invention, the alkali and peroxymonosulfate are added in solution form, wherein the molar ratio of hydroxide ions to peroxymonosulfate is 1 to 2:1.

[0014] According to one embodiment of the present invention, the alkali and peroxymonosulfate are added in solution form, wherein the molar ratio of hydroxide ions to peroxymonosulfate is 1.5:1.

[0015] According to one embodiment of the present invention, the peroxymonosulfate is potassium peroxymonosulfate.

[0016] According to one embodiment of the present invention, the copper-based material is copper oxide, and the dosage of copper oxide is 25~200 mg / L.

[0017] According to one embodiment of the present invention, the copper-based material is copper oxide, and the dosage of copper oxide is 50~150 mg / L.

[0018] According to one embodiment of the present invention, the copper-based material is copper oxide, and the dosage of copper oxide is 100 mg / L.

[0019] According to one embodiment of the present invention, the copper-based material is copper sulfide, and the dosage of copper sulfide is 15~100 mg / L.

[0020] According to one embodiment of the present invention, the copper-based material is copper sulfide, and the dosage of copper sulfide is 25~75 mg / L.

[0021] According to one embodiment of the present invention, the copper-based material is copper sulfide, and the dosage of copper sulfide is 50 mg / L.

[0022] According to one embodiment of the present invention, the water to be treated contains free radical-degraded pollutants.

[0023] According to one embodiment of the present invention, the free radical degradation pollutant comprises one or more of sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine.

[0024] Another aspect of this disclosure provides an alkali-enhanced copper-based material-activated peroxymonosulfate treatment apparatus. The apparatus includes: a reactor for containing an alkali, peroxymonosulfate, a copper-based material, and water to be treated, and for carrying out a reaction; an alkali addition device connected to the reactor for adding the alkali to the reactor; a peroxymonosulfate addition device connected to the reactor for adding the peroxymonosulfate to the reactor; a copper-based material addition device connected to the reactor for adding the copper-based material to the reactor; and a water to be treated addition device connected to the reactor for adding the water to be treated to the reactor.

[0025] According to an embodiment of the present invention, the copper-based material addition device is integrated with the reactor. The copper-based material is pre-placed in the reactor.

[0026] (III) Beneficial Effects

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] In this embodiment of the invention, an alkali agent, a copper-based material, and peroxymonosulfate are simultaneously added to the wastewater to be treated. The alkali agent and peroxymonosulfate act synergistically on the surface of the copper-based material, causing surface changes due to the strong alkali. These surface changes activate the continuous degradation capacity of the peroxymonosulfate system. In-situ alkali enhancement of the copper-based material activates the peroxymonosulfate system. Through in-situ alkali addition, the copper-based material is etched, continuously generating active sites, enhancing the adsorption and activation of peroxymonosulfate, and producing more sulfate and hydroxyl radicals, thus achieving effective degradation of pollutants.

[0029] 1. Under the action of an alkaline agent, a large number of hydroxyl groups are formed on the surface of copper oxide, which can induce the in-situ generation of abundant oxygen vacancies. Specifically, on the one hand, the coexistence of surface hydroxyl groups and oxygen vacancies produces a synergistic effect, which can significantly promote the adsorption and decomposition of peroxymonosulfate; on the other hand, the generation of oxygen vacancies and surface hydroxyl groups by in-situ alkaline etching is a process of active site regeneration, which effectively solves the problem of copper oxide deactivation and endows alkaline-enhanced copper oxide with the ability to activate peroxymonosulfate (OH-). - The continuous degradation capability of the CuO / PMS system.

[0030] 2. Under the action of an alkaline agent, the unique SS bonds on the surface of copper sulfide are reduced and broken. With the addition of peroxymonosulfate, the SS bonds are oxidized and restored. This process accelerates the electron transfer and circulation rate of the reaction, effectively promotes the regeneration of low-valent copper, achieves efficient decomposition of peroxymonosulfate, and endows alkali-enhanced copper sulfide with the activation of peroxymonosulfate (OH-). - The continuous degradation capability of the CuS / PMS system.

[0031] 3. OH - / CuO / PMS and OH -Under the in-situ alkali enhancement effect, peroxymonosulfate in the / CuS / PMS system is efficiently decomposed on the surface of copper-based materials, generating active species mainly composed of free radicals, thereby achieving complete removal of sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine from water.

[0032] 4. This invention offers advantages such as excellent treatment effect on new pollutants, mild reaction conditions, simple process flow, green and environmentally friendly operation, energy saving, and easy recycling and reuse. It achieves the goals of low dosage of oxidant and catalyst, high oxidant utilization rate, low metal ion leaching, and effluent pH compliance. It provides feasibility for advanced wastewater treatment and has good operability, making it widely applicable. Attached Figure Description

[0033] The above and other objects, features and advantages of the present invention will become clearer from the following description of embodiments of the invention with reference to the accompanying drawings.

[0034] Figure 1 Scanning electron microscope (SEM) images of copper oxide and copper sulfide used according to embodiments of the present invention are shown.

[0035] Figure 2 X-ray diffraction patterns of copper oxide and copper sulfide used according to embodiments of the present invention are shown.

[0036] Figure 3 The degradation effect of sulfamethoxazole in each system according to Example 1 of the present invention is shown in the figure.

[0037] Figure 4 The illustration shows the •OH and SO4 captured by DMPO in different systems according to Example 1 of the present invention. •− EPR spectrum.

[0038] Figure 5 The pH changes in different systems during the reaction process according to Example 1 of the present invention are shown.

[0039] Figure 6 The following diagram illustrates OH under different conditions according to Example 2 of the present invention. - Degradation effect of sulfamethoxazole in the CuO / PMS system.

[0040] Figure 7 The following diagram illustrates OH under different conditions according to Example 3 of the present invention. - Degradation effect of sulfamethoxazole in the CuS / PMS system.

[0041] Figure 8 The following is an illustration of OH according to Embodiment 4 of the present invention. - / CuO / PMS system and OH -Degradation effects of the CuS / PMS system on ibuprofen, atrazine, quinoline, and carbamazepine.

[0042] Figure 9 The illustration schematically shows the method and apparatus for treating peroxymonosulfate brine by alkali-strengthened copper-based materials according to Embodiment 6 of the present invention.

[0043] Figure 10 The schematic diagram illustrates a continuous flow device for sulfamethoxazole in the context of treating secondary effluent from a wastewater treatment plant under the conditions of long-term treatment according to Embodiments 7 and 8 of the present invention.

[0044] Figure 11 The OH in Embodiment 7 of the present invention is shown. - The effect of sulfamethoxazole in the long-term treatment of secondary effluent from a wastewater treatment plant using the / CuO / PMS system is illustrated.

[0045] Figure 12 The OH in Embodiment 8 of the present invention is shown. - The effect of sulfamethoxazole in the long-term treatment of secondary effluent from a wastewater treatment plant using the / CuS / PMS system is illustrated. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0047] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0048] Advanced oxidation technologies based on peroxymonosulfate (PFMS) offer core advantages such as low oxidant cost and safe and stable storage and transportation. They generate a variety of reactive oxygen species, primarily sulfate radicals, through activation regulation, demonstrating high efficiency and adaptability in the treatment of recalcitrant pollutants. This technology also features simple equipment, low energy consumption, and flexible operation, making it particularly suitable for complex wastewater systems. While transition metal activation systems are the mainstream approach, they generally face technical bottlenecks such as excessive oxidant and catalyst dosage, low oxidant utilization, metal ion dissolution, and excessive acidity in the effluent, limiting their engineering applications. Systematic breakthroughs through material enhancement and process optimization are urgently needed.

[0049] This invention aims to construct sustainable active sites by in-situ addition of alkali, thereby enhancing the performance of copper-based materials in activating peroxymonosulfate and building an alkali-enhanced copper-based material peroxymonosulfate activation system to achieve efficient removal of new, recalcitrant pollutants from water.

[0050] Based on this, embodiments of the present invention provide a water treatment method for in-situ alkali-enhanced copper-based materials to activate peroxymonosulfate. In this embodiment, an alkali agent, a copper-based material, and peroxymonosulfate are added to the water to be treated for reaction. The alkali agent is sodium hydroxide and / or potassium hydroxide; the copper-based material is copper oxide and / or copper sulfide. Through in-situ addition of the alkali agent, the copper-based material is etched in situ, continuously generating active sites, enhancing the adsorption and activation of peroxymonosulfate, and producing more abundant sulfate radicals and hydroxyl radicals. This achieves effective degradation of pollutants.

[0051] The above method has the advantages of mild reaction conditions, simple process flow and low cost.

[0052] In some embodiments of the present invention, the alkali, copper-based material, and persulfate can be added simultaneously to the water to be treated. It should be noted that "simultaneous addition" refers to a continuous and rapid sequence of additions, not to being limited to a single, extremely small point in time. The alkali-enhanced copper-based material-activated persulfate reaction occurs only when all three components are added to the water to be treated, resulting in the technical effect described in this application. In some cases, two of the components may be added to the water to be treated first, but since the alkali-enhanced copper-based material-activated persulfate reaction cannot occur, the reaction occurs only when the remaining third component is added. At this point, the presence of all three components in the water to be treated triggers the alkali-enhanced copper-based material-activated persulfate reaction, resulting in the technical effect described in this application. In this case, it can also be understood that the alkali, copper-based material, and persulfate are present simultaneously for the reaction described in this application to occur; this is what is meant by "simultaneous addition" in this application.

[0053] The free radical degradation pollutants mentioned in this application refer to pollutants that are decomposed into harmless substances based on the strong oxidizing properties of free radicals. These free radical degradation pollutants may include sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine. The embodiments of this invention can effectively remove sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine from water by simultaneously adding an alkali agent, a copper-based material, and peroxymonosulfate to an aqueous solution containing sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine, and stirring at room temperature. The copper-based catalyst is the aforementioned copper oxide or copper sulfide, which causes the degradation of sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine.

[0054] Alkali in-situ enhancement of the copper-based material activation peroxymonosulfate system involves in-situ etching of the copper-based material with alkali, continuously generating active sites, enhancing the adsorption and activation of peroxymonosulfate, and producing more sulfate and hydroxyl radicals. These radicals react with pollutants in water, such as sulfamethoxazole, ibuprofen, atrazine, quinoline, or carbamazepine, through reactions such as hydroxylation, ketation, decarboxylation, demethylation, side-chain decarboxylation, and aryl epoxidation, thereby achieving effective degradation of pollutants.

[0055] This invention also provides an alkali-enhanced copper-based material-activated peroxymonosulfate treatment device. The device includes: a reactor for containing an alkali, peroxymonosulfate, a copper-based material, and water to be treated, and for carrying out the reaction; an alkali addition device connected to the reactor for adding the alkali; a peroxymonosulfate addition device connected to the reactor for adding the peroxymonosulfate; a copper-based material addition device connected to the reactor for adding the copper-based material; and a water to be treated addition device connected to the reactor for adding the water to be treated. In some cases, one component can be added to the water to be treated or the reactor first. Therefore, the corresponding two addition devices can be combined in the design. For example, the copper-based material addition device and the reactor can be combined into one, or the peroxymonosulfate addition device and the water to be treated addition device can be combined in the design.

[0056] This invention provides a method for constructing a continuous flow system using an in-situ alkali-enhanced copper-based material to activate a peroxymonosulfate system, thereby achieving long-term removal of sulfamethoxazole from secondary effluent of a wastewater treatment plant. The method includes: fixing a copper-based material between layers of degreased cotton to form a reaction column; and simultaneously introducing the secondary effluent containing alkali and sulfamethoxazole, along with a peroxymonosulfate solution, into the reaction column via two separate pipelines, so that the sulfamethoxazole in the final effluent is degraded.

[0057] The present invention will be further described below through specific embodiments. The following examples specifically illustrate the method and application of activating peroxy monosulfate in the above-mentioned alkali-in-situ reinforced copper-based material. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

[0058] Example 1:

[0059] Different systems (peroxymonosulfate (PMS), alkali (OH) - ), copper-based materials (CuO or CuS), OH - / PMS, CuO / PMS, CuS / PMS, OH - / CuO、OH - / CuS、OH - / CuO / PMS, OH -The effect of CuS / PMS on the removal of sulfamethoxazole (SMX) from treated water.

[0060] PMS system: Peroxymonosulfate is added to an aqueous solution containing sulfamethoxazole for reaction.

[0061] OH - System: Add the alkali to an aqueous solution containing sulfamethoxazole and react.

[0062] CuO system: CuO is added to an aqueous solution containing sulfamethoxazole for reaction.

[0063] CuS system: CuS is added to an aqueous solution containing sulfamethoxazole for reaction.

[0064] OH - / PMS system: The alkali and peroxymonosulfate are added to an aqueous solution containing sulfamethoxazole for reaction.

[0065] CuO / PMS system: CuO and peroxymonosulfate are added to an aqueous solution containing sulfamethoxazole for reaction.

[0066] CuS / PMS system: CuS and peroxymonosulfate are added to an aqueous solution containing sulfamethoxazole for reaction.

[0067] OH - / CuO: Add the alkali and CuO to an aqueous solution containing sulfamethoxazole and react.

[0068] OH - / CuS system: Add alkali and CuS to an aqueous solution containing sulfamethoxazole for reaction.

[0069] OH - / CuO / PMS system: Alkali, CuO and peroxymonosulfate are added to an aqueous solution containing sulfamethoxazole and reacted.

[0070] OH - / CuS / PMS system: Alkali, CuS and peroxymonosulfate are added to an aqueous solution containing sulfamethoxazole for reaction.

[0071] Experimental conditions: In this embodiment, potassium persulfate (PMS) was specifically used, and more specifically, a compound salt of potassium persulfate was used, with a mass fraction of potassium persulfate of 42%. The alkali was sodium hydroxide, and the molar ratio of sodium hydroxide to potassium persulfate was 1.5:1. Specifically, the dosage for the CuO-containing system was 0.6 mM alkali, 0.4 mM potassium persulfate, and 100 mg / L CuO; the dosage for the CuS-containing system was 0.3 mM alkali, 0.2 mM PMS, and 50 mg / L CuS; the concentration of sulfamethoxazole in the water to be treated in each system was 5 mg / L.

[0072] Figure 1 The images show scanning electron microscope (SEM) images of the copper oxide and copper sulfide products used in the embodiments of the present invention. From the images, CuO and CuS appear as irregular micro- and nano-sized particles.

[0073] Figure 2 The images show the X-ray diffraction patterns of the copper oxide and copper sulfide products used in the embodiments of the present invention. The characteristic diffraction peaks of the CuO and CuS products correspond to the standard CuO (PDF 45-0937) and CuS (PDF 06-0464), and the diffraction peaks are clear and strong.

[0074] The concentrations of sulfamethoxazole in each system at each stage were measured using high-performance liquid chromatography (HPLC), and the degradation effect of sulfamethoxazole was obtained, as shown in the figure. Figure 3 (In this application, the initial concentration is represented by C0, and the concentration measured after the reaction begins is represented by C.) t express)

[0075] The ·OH and SO4 captured by DMPO (5,5-dimethyl-dimethyl-1-pyrrolidine-N-oxide) in the above systems •− EPR spectrum as Figure 4 As shown.

[0076] The pH changes of different systems during the reaction are as follows: Figure 5 As shown.

[0077] Depend on Figure 3 It is evident that peroxymonosulfate, alkali, and copper-based materials themselves cannot degrade sulfamethoxazole. Not only do the alkali and copper-based materials individually exhibit negligible activation effects on peroxymonosulfate, but the alkali-treated copper-based materials also show no significant adsorption effect on sulfamethoxazole. Only when the alkali, copper-based material, and peroxymonosulfate coexist can 100% degradation of sulfamethoxazole be achieved. When CuO is used as the copper-based material, sulfamethoxazole degrades rapidly within 15 minutes; when CuS is used, sulfamethoxazole is essentially decomposed within 1 minute.

[0078] Depend on Figure 4It is evident that the alkali-in-situ strengthening of copper-based materials can activate the peroxymonosulfate system (OH). - / CuO / PMS system, OH - The CuS / PMS system generates active species ·OH and SO4. •− Furthermore, the spectral signal intensity captured by EPR is significantly higher than that of PMS, OH- / PMS, and copper-based material / PMS systems. Analysis reveals that in the presence of an alkaline agent, copper-based materials can be etched in situ to create a large number of regenerable active sites, such as oxygen vacancies, surface hydroxyl groups, and low-valence copper ions. This promotes the continuous decomposition of peroxymonosulfate, generating more free radicals. Under the continuous attack of free radicals, sulfamethoxazole is effectively degraded into small-molecule, non-toxic substances.

[0079] Depend on Figure 5 It is evident that by monitoring pH changes during the reaction process, the introduction of alkali effectively alleviated the problem of excessive acidity in the effluent of the peroxymonosulfate system, and stabilized the effluent pH within the compliant range of 6-9 (GB 18918-2002).

[0080] Example 2:

[0081] In OH - The effect of different molar ratios of alkali and peroxymonosulfate on the degradation of sulfamethoxazole in water in the CuO / PMS system.

[0082] Sodium hydroxide, copper oxide, and potassium persulfate were simultaneously added to five portions of aqueous solutions containing sulfamethoxazole, and each portion was then reacted in a mechanically stirred container at room temperature. The molar ratios of sodium hydroxide and potassium persulfate in the five portions were 0.5:1, 1:1, 1.5:1, 2:1, and 2.5:1, respectively, with the same amount of potassium persulfate (0.4 mM) and the same amount of CuO (100 mg / L). The concentration of sulfamethoxazole was 5 mg / L.

[0083] The concentrations of sulfamethoxazole in each system at each stage were measured using high-performance liquid chromatography (HPLC). The removal efficiency curves of sulfamethoxazole by different molar ratios of alkali and persulfate are shown in the figure below. Figure 6 As shown in Figure a, after 20 minutes of reaction, when OH... - When the PMS ratio was 0.5:1, the degradation rate of sulfamethoxazole was 46.1%; when OH... - When the PMS ratio is 1:1, the degradation rate of sulfamethoxazole is 88.9%; when OH... - When the PMS ratio is 1.5:1, the degradation rate of sulfamethoxazole is 100%; when OH... - When the PMS ratio is 2:1, the degradation rate of sulfamethoxazole is 100%; when OH... -When the PMS ratio was 0.5:1, the degradation rate of sulfamethoxazole was 79.2%. This indicates that with the increase of OH... - With increasing PMS ratio, the degradation of sulfamethoxazole initially increases and then decreases, OH - A ratio that is too high or too low with PMS is not conducive to the degradation and removal of sulfamethoxazole.

[0084] In OH - Effects of different copper oxide dosages on the degradation of sulfamethoxazole in water within the CuO / PMS system.

[0085] Sodium hydroxide, copper oxide, and potassium persulfate were simultaneously added to five portions of aqueous solutions containing sulfamethoxazole, and each portion was then placed in a mechanical stirrer at room temperature for reaction. The amounts of copper oxide added in the five portions were 25, 50, 100, 150, and 200 mg / L, respectively. The molar ratio of sodium hydroxide to potassium persulfate was the same (1.5:1), and the amount of potassium persulfate was the same (0.4 mM molar concentration). The concentration of sulfamethoxazole was 5 mg / L.

[0086] The concentrations of sulfamethoxazole in each system at each stage were measured using high-performance liquid chromatography (HPLC). The curves showing the removal efficiency of sulfamethoxazole with different copper oxide dosages are shown below. Figure 6 As shown in b, after a reaction time of 20 minutes, the degradation rate of sulfamethoxazole was 53.2% when the CuO dosage was 25 mg / L; 90.9% when the CuO dosage was 50 mg / L; 100% when the CuO dosage was 100 mg / L; 150% when the CuO dosage was 150 mg / L; and 100% when the CuO dosage was 200 mg / L. Therefore, the degradation rate of sulfamethoxazole gradually increases with increasing CuO dosage. Considering the overall economic cost, a CuO dosage of 100 mg / L is preferable.

[0087] Under the action of an alkaline agent, a large number of hydroxyl groups are formed on the surface of copper oxide, which can induce the in-situ generation of abundant oxygen vacancies. Specifically, on the one hand, the coexistence of surface hydroxyl groups and oxygen vacancies produces a synergistic effect, which can significantly promote the adsorption and decomposition of peroxymonosulfate; on the other hand, the generation of oxygen vacancies and surface hydroxyl groups by in-situ alkaline etching is a process of active site regeneration, which effectively solves the problem of copper oxide deactivation and endows alkaline-enhanced copper oxide with the ability to activate peroxymonosulfate (OH-). - The continuous degradation capability of the CuO / PMS system.

[0088] Example 3:

[0089] In OH -The effect of different molar ratios of alkali and peroxymonosulfate on the degradation of sulfamethoxazole in water in the CuS / PMS system.

[0090] Sodium hydroxide, copper sulfide, and potassium persulfate were simultaneously added to five portions of aqueous solutions containing sulfamethoxazole, and then each portion was reacted in a mechanically stirred container at room temperature. The molar ratios of sodium hydroxide and potassium persulfate in the five portions were 0.5:1, 1:1, 1.5:1, 2:1, and 2.5:1, respectively, and the amount of potassium persulfate used was the same (0.2 mM molar concentration), and the amount of CuS used was the same (50 mg / L). The concentration of sulfamethoxazole was 5 mg / L.

[0091] The curves showing the removal efficiency of sulfamethoxazole by alkali and peroxymonosulfate at different molar concentrations are shown below. Figure 7 As shown in a, the reaction takes 5 minutes, when OH... - When the PMS ratio was 0.5:1, the degradation rate of sulfamethoxazole was 34.3%; when OH... - When the PMS ratio is increased to 1:1 or higher, the degradation rate of sulfamethoxazole is 100%. Considering that the effluent pH is best maintained between 6 and 9, OH... - A ratio of 1.5:1 to PMS is not ideal, as both are too high and too low.

[0092] In OH - Effects of different copper sulfide dosages on the degradation of sulfamethoxazole in water within the CuS / PMS system.

[0093] Sodium hydroxide, copper sulfide, and 42% potassium persulfate were simultaneously added to five portions of aqueous solutions containing sulfamethoxazole, respectively, and then the mixtures were reacted separately in mechanical stirrers at room temperature. The amounts of copper sulfide added in the five portions were 15, 25, 50, 75, and 100 mg / L, respectively. The molar ratio of sodium hydroxide to potassium persulfate was the same (1.5:1), and the amount of potassium persulfate was the same (0.2 mM). The concentration of sulfamethoxazole was 5 mg / L.

[0094] The effect curves of different copper oxide dosages on the removal of sulfamethoxazole are shown in the figure. Figure 7 As shown in b, complete degradation of sulfamethoxazole can be achieved with a CuS dosage of only 15 mg / L. However, the degradation rate of sulfamethoxazole first increases and then decreases with increasing CuS dosage. When the CuS dosage is 15 mg / L, the degradation rate constant of sulfamethoxazole is 5.53 × 10⁻⁶. -2 s -1 When the CuS dosage is 25 mg / L, the degradation rate constant of sulfamethoxazole is 6.64 × 10⁻⁶. -2 s -1When the CuS dosage is 50 mg / L, the degradation rate constant of sulfamethoxazole is 6.88 × 10⁻⁶. -2 s -1 When the CuS dosage is 75 mg / L, the degradation rate constant of sulfamethoxazole is 5.53 × 10⁻⁶. -2 s -1 When the CuS dosage is 100 mg / L, the degradation rate constant of sulfamethoxazole is 5.48 × 10⁻⁶. -2 s -1 Therefore, it is evident that both excessively high and excessively low CuS dosages are detrimental, with 50 mg / L being the optimal level.

[0095] In this embodiment, the copper sulfide-based strengthening method involves the reduction and breakage of the unique SS bonds on the copper sulfide surface under the action of an alkaline agent. With the addition of peroxymonosulfate, these SS bonds are oxidized and restored. This process accelerates the electron transfer and circulation rate of the reaction, effectively promoting the regeneration of low-valent copper and achieving efficient decomposition of peroxymonosulfate. This process endows the alkaline-strengthened copper sulfide with the ability to activate peroxymonosulfate (OH-). - The continuous degradation capability of the CuS / PMS system.

[0096] Example 4:

[0097] OH - / CuO / PMS system and OH - The degradation effect of the / CuS / PMS system on a variety of recalcitrant new pollutants, including ibuprofen (IBP), atrazine (ATZ), quinoline (QNL), and carbamazepine (CBZ).

[0098] Sodium hydroxide, a copper-based material, and potassium persulfate were simultaneously added to aqueous solutions containing ibuprofen, atrazine, quinoline, or carbamazepine, respectively, and then the solutions were placed in mechanically stirred at room temperature. The molar ratio of sodium hydroxide to potassium persulfate was 1.5:1. - In the CuO / PMS system, the molar concentration of potassium persulfate was always 0.4 mM, and the amount of CuO used was always 100 mg / L. In OH... - In the CuS / PMS system, the molar concentration of potassium persulfate is the same at 0.2 mM, and the amount of CuS is the same at 50 mg / L. The concentration of the above-mentioned pollutants is the same at 5 mg / L.

[0099] The concentrations of pollutants in each system at each stage were measured using high-performance liquid chromatography. Figure 8 To implement the OH of the present invention - / CuO / PMS system and OH -The schematic diagram illustrates the degradation effects of the / CuS / PMS system on ibuprofen (IBP), atrazine (ATZ), quinoline (QNL), and carbamazepine (CBZ). It can be seen that OH... - / CuO / PMS system and OH - The CuS / PMS system exhibits excellent degradation effects on average for ibuprofen, atrazine, quinoline, and carbamazepine.

[0100] Example 5:

[0101] This embodiment differs from Embodiment 4 in that it uses one or more of potassium persulfate, sodium persulfate, and calcium monopersulfate as peroxymonosulfate. For example, a mixture containing sodium persulfate and calcium monopersulfate is used as peroxymonosulfate. Sodium hydroxide and / or potassium hydroxide are used as the alkali. For example, a mixed solution containing sodium hydroxide and potassium hydroxide is added as the alkali. When the above materials are combined, the amount added is calculated based on the sum of the molar concentrations of the composition; for example, the molar ratio of hydroxide ions to persulfate ions is the same, which is 1.5:1. The amounts of sodium hydroxide and potassium hydroxide can be flexibly adjusted. Copper oxide and copper sulfide are used as copper-based materials. For example, a mixture containing copper oxide and copper sulfide in a 1:1 molar ratio is used as the copper-based material.

[0102] Using the above systems as reactants, excellent degradation effects can also be achieved on average for sulfamethoxazole, ibuprofen, atrazine, quinoline, and carbamazepine.

[0103] Example 6:

[0104] Figure 9 This is a schematic diagram of an alkali-reinforced copper-based material-activated peroxymonosulfate brine treatment device according to this embodiment. Figure 9 As shown in Figure a, the apparatus comprises: a reactor for containing an alkali, peroxymonosulfate, a copper-based material, and water to be treated, and for carrying out the reaction; an alkali adding device connected to the reactor for adding the alkali; a peroxymonosulfate adding device connected to the reactor for adding peroxymonosulfate; a copper-based material adding device connected to the reactor for adding the copper-based material; and a water to be treated adding device connected to the reactor for adding the water to be treated. In use, the alkali, copper-based material, peroxymonosulfate, and water to be treated are jointly injected into the reactor for the reaction.

[0105] like Figure 9 As shown in b, in this embodiment, the copper-based material addition device and the reactor are integrated, with the copper-based material pre-placed in the reactor. During use, alkali, peroxymonosulfate, and water to be treated are continuously added to the reactor containing the pre-placed copper-based material, achieving continuous treatment of the water.

[0106] The secondary effluent used in Examples 7 and 8 below is the effluent from the secondary sedimentation tank of a wastewater treatment plant in a city in Beijing before deep treatment. The total nitrogen content in the secondary effluent is 1.46 mg / L, the total phosphorus content is 0.42 mg / L, the COD content is 17 mg / L, the TOC content is 3.89 mg / L, and the pH value is 7.67. Eighteen new pollutants, mainly sulfonamides, were detected, with the highest concentration reaching 53.56 ng / L.

[0107] Figure 10 a is based on OH in the following embodiment 7 of the present invention. - A schematic diagram of a continuous flow device for sulfamethoxazole in a CuO / PMS system for long-term treatment of secondary effluent from a wastewater treatment plant. Figure 10 b is based on OH in the following embodiment 8 of the present invention. - A schematic diagram of a continuous flow device for sulfamethoxazole in a CuS / PMS system for long-term treatment of secondary effluent from a wastewater treatment plant.

[0108] Example 7:

[0109] Based on OH - The effect of the CuO / PMS system on the long-term treatment of sulfamethoxazole in the secondary effluent of wastewater treatment plants.

[0110] The specific construction and operation method and process of the continuous flow apparatus are as follows: A cylindrical plexiglass tube with a diameter of 2 cm, a height of 6.8 cm, and a volume of approximately 21 mL is filled with defatted cotton. An aqueous solution containing 400 mg of copper oxide is dropped between the cotton layers to form a reaction column. Then, secondary effluent containing sodium hydroxide and sulfamethoxazole (0.25 mL / min) and a 42% potassium persulfate solution (0.25 mL / min) are simultaneously introduced into the reaction column at a flow rate of 0.5 mL / min. The hydraulic residence time in the reaction column is approximately 42 min. The molar ratio of sodium hydroxide to potassium persulfate is 1.5:1, and the amount of potassium persulfate used is 0.5 mM. The concentration of sulfamethoxazole is 5 mg / L.

[0111] Figure 11 This indicates that the continuous flow unit can operate stably for at least 12 days, during which the removal rate of sulfamethoxazole in the secondary effluent remains above 95%. Figure 11 a), with an average mineralization rate of 64.34% ( Figure 11 b); PMS utilization rate remained above 84% ( Figure 11 c) The average leaching concentration of copper ions was stably controlled below 0.1 mg / L, and the pH value of the effluent was stably maintained at around 7. Figure 11d). The above results fully demonstrate that the copper oxide-activated peroxymonosulfate technology based on alkaline in-situ enhancement is environmentally friendly. The excellent performance of this system not only stems from its complete degradation of pollutants, but also benefits from its high PMS utilization rate and trace Cu ion residue characteristics.

[0112] The copper-based material in this embodiment can be separated after use and reused with alkali and peroxymonosulfate, which has the technical advantages of easy recycling and reuse.

[0113] Example 8:

[0114] Based on OH - The effect of the CuS / PMS system on the long-term treatment of sulfamethoxazole in the secondary effluent of wastewater treatment plants.

[0115] The specific construction and operation method and process of the continuous flow apparatus are as follows: A cylindrical plexiglass tube with a diameter of 2 cm, a height of 6.8 cm, and a volume of approximately 21 mL is filled with degreased cotton. An aqueous solution containing 200 mg of copper sulfide is dropped between the cotton columns to form a reaction column. Then, secondary effluent containing sodium hydroxide and sulfamethoxazole (0.25 mL / min) and a 42% potassium persulfate solution (0.25 mL / min) are simultaneously introduced into the reaction column at a flow rate of 0.5 mL / min. The hydraulic residence time in the reaction column is approximately 42 min. The molar ratio of sodium hydroxide to potassium persulfate is 1.5:1, and the amount of potassium persulfate used is 0.5 mM. The concentration of sulfamethoxazole is 5 mg / L.

[0116] Figure 12 This indicates that the continuous flow unit can operate stably for at least 12 days, during which the removal rate of sulfamethoxazole in the secondary effluent remains above 95%. Figure 12 a), with an average mineralization rate of 70.56% ( Figure 12 b); PMS utilization rate remained above 91% ( Figure 12 c) The average leaching concentration of copper ions was stably controlled below 0.1 mg / L, and the pH value of the effluent was stably maintained at around 7. Figure 12 d). The above results fully demonstrate that the copper sulfide-activated peroxymonosulfate technology based on alkaline in-situ enhancement is environmentally friendly. The excellent performance of this system not only stems from its complete degradation of pollutants, but also benefits from its high PMS utilization rate and trace Cu ion residue characteristics.

[0117] The alkali-strengthened copper-based material activated peroxymonosulfate treatment method and apparatus of this invention are used to solve the technical problems of excessive dosage of oxidant and catalyst, poor effect, low utilization rate of oxidant, metal ion dissolution and excessive acidity of effluent in traditional transition metal activated peroxymonosulfate systems.

[0118] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for treating peroxymonosulfate brine by activating alkali-reinforced copper-based materials, characterized in that, The method includes: adding an alkaline agent, a copper-based material, and peroxymonosulfate to the water to be treated; Specifically, the copper-based material is etched in situ by in-situ addition of an alkali agent, thereby continuously generating active sites on the surface of the copper-based material; the active sites include oxygen vacancies and / or surface hydroxyl groups. The alkaline agent is sodium hydroxide and / or potassium hydroxide; The copper-based material is copper oxide and / or copper sulfide; The peroxymonosulfate is one or a combination of two or more of potassium peroxymonosulfate, sodium peroxymonosulfate, and calcium peroxymonosulfate.

2. The method according to claim 1, characterized in that, The alkali and peroxymonosulfate are added in solution form, wherein the molar ratio of hydroxide ions to peroxymonosulfate is 0.5~2.5:

1.

3. The method according to claim 1, characterized in that, The alkali and peroxymonosulfate are added in solution form, wherein the molar ratio of hydroxide ions to peroxymonosulfate is 1~2:

1.

4. The method according to claim 1, characterized in that, The peroxymonosulfate is potassium peroxymonosulfate.

5. The method according to claim 1, characterized in that, The copper-based material is copper oxide, and the dosage of copper oxide is 25~200 mg / L.

6. The method according to claim 1, characterized in that, The copper-based material is copper oxide, and the dosage of copper oxide is 50~150 mg / L.

7. The method according to claim 1, characterized in that, The copper-based material is copper sulfide, and the dosage of copper sulfide is 15~100 mg / L.

8. The method according to claim 1, characterized in that, The copper-based material is copper sulfide, and the dosage of copper sulfide is 25~75 mg / L.

9. The method according to claim 1, characterized in that, The water to be treated contains pollutants that are degraded by free radicals.

10. A device for treating peroxymonosulfate brine using alkali-reinforced copper-based materials, characterized in that, The device includes: The reactor is used to contain alkali, peroxymonosulfate, copper-based materials, and water to be treated, and to carry out the reaction. An alkali addition device, connected to the reactor, is used to add alkali to the reactor; A peroxymonosulfate addition device, connected to the reactor, is used to add peroxymonosulfate to the reactor; A copper-based material adding device, connected to the reactor, is used to add copper-based materials to the reactor; A device for adding water to be treated is connected to the reactor and is used to add water to be treated to the reactor; The alkali addition device is configured to perform in-situ etching on the copper-based material by in-situ addition of alkali, thereby continuously generating active sites on the surface of the copper-based material. The active sites include oxygen vacancies and / or surface hydroxyl groups.

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