Resource application method of zeolite-based material with two-stage synergism of heavy metal adsorption and antibiotic catalytic degradation

Abstract

The invention discloses a resource application method of a zeolite-based material with two-stage synergism of heavy metal adsorption and antibiotic catalytic degradation, and belongs to the field of wastewater treatment. The method comprises the following steps: (1) adding zeolite into wastewater containing heavy metal ions, uniformly mixing, oscillating, and adsorbing to remove the heavy metal ions in the wastewater; (2) sequentially washing, filtering and drying the zeolite adsorbed with the heavy metal ions to obtain a zeolite-based catalyst; and (3) adding the zeolite-based catalyst into the wastewater containing the antibiotics, adding an oxidant, uniformly mixing, and oscillating to realize catalytic degradation of the antibiotics in the wastewater. According to the invention, heavy metal ions are removed by using the cation exchange performance of zeolite, and the zeolite adsorbing heavy metals is directly used as a catalyst to degrade antibiotics, so that the resource utilization of heavy metal pollutants is realized. The method shows excellent heavy metal adsorption performance and antibiotic catalytic degradation effect, and has the advantages of wide application range, simple process and the like.

Description

Technical Field

[0001] The invention belongs to the field of wastewater treatment, and specifically relates to a resource application method of a zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics. Background Art

[0002] In the course of industrial and agricultural production activities, humans inevitably produce various pollutants that are harmful to the environment. Among them, heavy metals and antibiotic pollutants pose a serious threat to human health and the ecosystem due to their significant biological toxicity, chemical stability and difficulty in degradation. Among the existing treatment methods, the adsorption method shows a good application effect in removing heavy metal pollutants, while the advanced oxidation method is mainly used in the degradation treatment of antibiotic wastewater. However, it is still difficult to organically integrate the two functions of heavy metal removal and antibiotic catalytic degradation into a single material or process method. In addition, the discarded adsorbent after adsorbing heavy metals is also a hazardous waste and is in urgent need of further harmless treatment. The Chinese invention patent with application publication number CN104496092A discloses a method for treating organic wastewater by reusing heavy metal adsorbed saturated activated carbon, and proposes to use heavy metal adsorbed saturated activated carbon as a catalyst for electrochemical catalytic degradation of organic pollutants, but this method requires supporting electrochemical equipment, and the process complexity and equipment investment are high, and the sustainability is poor. The Chinese invention patent with application publication number CN112340830A discloses a catalyst using waste adsorbent after adsorption-desorption as raw material in the treatment of high-salt organic wastewater with activated persulfate, and proposes mixing the waste adsorbent after multiple adsorption of heavy metal ions-desorption with a nitrogen source, and recycling it through high-temperature pyrolysis as a catalyst for catalytic degradation of high-salt organic wastewater. However, this method requires multiple adsorption-desorption cycles and pyrolysis treatment, and the operation steps are cumbersome, the energy consumption is high, and it is difficult to achieve large-scale application. Summary of the invention

[0003] Based on the above technical problems, the present invention proposes a resource application method of a zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics.

[0004] The technical solution adopted by the present invention is:

[0005] A resource application method of a zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics, comprising the following steps:

[0006] (1) adding zeolite to wastewater containing heavy metal ions, mixing well and then oscillating to adsorb and remove the heavy metal ions in the wastewater;

[0007] (2) washing, filtering and drying the zeolite adsorbed with heavy metal ions in sequence to obtain a zeolite-based catalyst;

[0008] (3) A zeolite-based catalyst is added to wastewater containing antibiotics, and an oxidant is added at the same time. The mixture is mixed evenly and then shaken to achieve catalytic degradation of the antibiotics in the wastewater.

[0009] Preferably, in step (1): the zeolite is a natural zeolite or an artificially synthesized magnetic zeolite; the types of zeolites include type A, type X, type Y, type Beta, type ZSM, mordenite and clinoptilolite.

[0010] Preferably, in step (1): the heavy metal ions are one or more of copper, cobalt, nickel, manganese and iron ions.

[0011] Preferably, in step (1): the heavy metal ion concentration in the wastewater is 20-500 mg / L, the pH value of the wastewater is 4-7, and the volume ratio of the zeolite addition mass to the wastewater is 0.5-5:1 g / L.

[0012] Preferably, in step (1), the oscillation temperature is 10-50°C, the oscillation speed is 50-250 rpm, and the oscillation time is 0.5-24h.

[0013] Preferably, in step (2): the washing treatment uses anhydrous ethanol and deionized water in sequence, and the anhydrous ethanol and deionized water are washed 2-3 times respectively; the drying is carried out in a vacuum drying oven, the drying temperature is 60-105°C, and the drying time is 6-12h.

[0014] Preferably, in step (3): the antibiotic is one or more of tetracycline, ofloxacin, tetracycline hydrochloride, and ciprofloxacin.

[0015] Preferably, in step (3): the concentration of the antibiotic in the wastewater is 5-50 mg / L, the pH value of the wastewater is 4-9, and the volume ratio of the added mass of the zeolite-based catalyst to the wastewater is 0.1-1:1 g / L.

[0016] Preferably, in step (3): the oxidant is one of potassium peroxymonosulfate, potassium peroxydisulfate or hydrogen peroxide, and the volume ratio of the oxidant addition amount to the wastewater is 0.2-50 mmol / L.

[0017] Preferably, in step (3): the oscillation temperature is 10-50°C, the oscillation speed is 50-250 rpm, and the oscillation time is 5-120 min.

[0018] The beneficial technical effects of the present invention are as follows:

[0019] The present invention innovatively utilizes the cation exchange properties of zeolite, uses it as an adsorbent to remove heavy metal ions in wastewater, fixes heavy metal ions in the zeolite lattice through the ion exchange mechanism, realizes in-situ loading of heavy metals, and constructs a zeolite-based catalyst. The zeolite-based catalyst is used to remove antibiotics in wastewater, and can effectively catalyze the degradation of antibiotics in wastewater without additional heat treatment or chemical modification process, and has a high degradation efficiency. The present invention improves the resource utilization efficiency of heavy metal ions in wastewater, and realizes the unity of pollutant reduction and resource utilization.

[0020] The present invention also has significant technical advantages and good industrial application potential, which are specifically reflected in the following aspects: (1) It has a wide range of applications and can be applied to most natural and synthetic zeolites with cation exchange properties. The raw material sources are abundant and do not require pretreatment or modification; (2) The process flow is simple, and a highly active catalyst can be prepared only through a simple adsorption process, which significantly reduces energy consumption; (3) It has excellent adsorption performance and exhibits high adsorption capacity for heavy metal ions; (4) It has excellent catalytic performance and can achieve efficient degradation of antibiotics in a short time; (5) The entire process complies with the principles of green chemistry and meets my country's sustainable development requirements. Based on the above advantages, the present invention shows broad development prospects and practical application value in the fields of environmental pollution control and resource recycling. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic flow chart of the resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics of the present invention;

[0022] Figure 2 X-ray diffraction patterns of type A zeolite and magnetic type A zeolite used in Example 1 and Example 2 of the present invention, respectively;

[0023] Figure 3 This is a comparison chart of the adsorption effects of the zeolite-based adsorbents used in Examples 1 to 5 of the present invention on heavy metal ions;

[0024] Figure 4 This is a comparison chart of the catalytic degradation effects of the zeolite-based catalysts used in Examples 1 to 5 of the present invention on antibiotics. DETAILED DESCRIPTION

[0025] Zeolite, as a typical type of silicon-aluminum-based porous material, has been widely used in wastewater treatment and energy chemical industry due to its excellent specific surface area and simple preparation process. Zeolite has excellent cation exchange properties and can undergo reversible ion exchange reactions with heavy metal ions, showing excellent heavy metal adsorption and removal effects. However, due to the lack of specific organic functional groups and transition metal elements, traditional zeolites are difficult to achieve efficient removal of antibiotics and cannot meet the needs of synergistic removal of two types of pollutants at the same time. Therefore, exploring a new method that organically combines the heavy metal adsorption function of zeolite with the catalytic degradation ability of antibiotics to achieve waste resource utilization and avoid secondary pollution has broad application prospects.

[0026] Based on this, the present invention proposes a resource application method of a zeolite-based material with two-level synergy of heavy metal adsorption and antibiotic catalytic degradation. This method can organically integrate heavy metal removal and antibiotic catalytic degradation into the same process by constructing a two-level synergistic process of "heavy metal adsorption-antibiotic catalytic degradation", and has the advantages of simple process and low cost.

[0027] The present invention can synergistically treat heavy metal ions and antibiotics in wastewater. First, the excellent cation exchange properties of zeolite-based adsorbents are fully utilized to achieve efficient removal of heavy metal pollutants. Furthermore, the zeolite material loaded with heavy metals is directly used as a catalyst to achieve efficient degradation of antibiotics, which not only effectively solves the secondary pollution problem in traditional treatment methods, but also realizes the resource transformation and recycling of heavy metal pollutants in the wastewater treatment process. The innovativeness of the technical route of the present invention is reflected in the integration of process and the synergistic treatment of pollutants, providing an efficient, economical and environmentally friendly technical solution for the field of environmental governance.

[0028] The present invention will be further described below in conjunction with specific embodiments.

[0029] Example 1

[0030] (1) 0.09 g of type A zeolite-based adsorbent was added to 50 mL of wastewater containing 85 mg / L copper ions (pH 5), mixed evenly, and shaken at 150 rpm at 25 °C for 2 h.

[0031] (2) The type A zeolite-based adsorbent that has adsorbed copper ions was washed three times with anhydrous ethanol and deionized water, respectively, and dried in a vacuum drying oven at 60° C. for 8 h to obtain a type A zeolite-based catalyst loaded with copper ions.

[0032] (3) 0.005 g of copper ion-loaded A-type zeolite-based catalyst was added to 50 mL of wastewater (pH 6.5) containing 10 mg / L tetracycline, and potassium peroxymonosulfate (1 mmol / L) was added at the same time. The mixture was mixed well and shaken at 200 rpm at 25°C for 1 h.

[0033] Example 2

[0034] (1) 0.2 g of magnetic type A zeolite-based adsorbent was added to 100 mL of wastewater containing 200 mg / L copper ions (pH 4), mixed evenly, and shaken at 150 rpm at 25°C for 8 h.

[0035] (2) The magnetic A-type zeolite-based adsorbent that has adsorbed copper ions is washed twice with anhydrous ethanol and deionized water respectively, and dried in a vacuum drying oven at 80° C. for 7 h to obtain a magnetic A-type zeolite-based catalyst loaded with copper ions.

[0036] (3) 0.005 g of a copper-loaded magnetic A-type zeolite-based catalyst was added to 50 mL of wastewater (pH 6) containing 20 mg / L tetracycline, and 30% hydrogen peroxide (10 mmol / L) was added at the same time. The mixture was mixed well and shaken at 200 rpm at 25°C for 1 h.

[0037] Example 3

[0038] (1) 0.1 g of magnetic type A zeolite-based adsorbent was added to 50 mL of wastewater containing 100 mg / L copper ions (pH 4), mixed evenly, and shaken at 150 rpm at 25 °C for 8 h.

[0039] (2) The magnetic A-type zeolite-based adsorbent that has adsorbed copper ions was washed three times with anhydrous ethanol and deionized water respectively, and dried in a vacuum drying oven at 100° C. for 6 h to obtain a magnetic A-type zeolite-based catalyst loaded with copper ions.

[0040] (3) 0.02 g of a copper-loaded magnetic A-type zeolite-based catalyst was added to 200 mL of wastewater (pH 7) containing 30 mg / L tetracycline, and potassium peroxymonosulfate (0.5 mmol / L) was added at the same time. The mixture was mixed well and shaken at 200 rpm at 25°C for 40 min.

[0041] Example 4

[0042] (1) 0.1 g of type A zeolite-based adsorbent was added to 50 mL of wastewater containing 200 mg / L copper ions (pH 7), mixed evenly, and shaken at 150 rpm at 25 °C for 8 h.

[0043] (2) The A-type zeolite-based adsorbent that has adsorbed copper ions was washed three times with anhydrous ethanol and deionized water, and dried in a vacuum drying oven at 60° C. for 12 h to obtain an A-type zeolite-based catalyst loaded with copper ions.

[0044] (3) 0.005 g of a copper ion-loaded A-type zeolite-based catalyst was added to 50 mL of wastewater (pH 3) containing 5 mg / L ofloxacin, and potassium persulfate (1 mmol / L) was added at the same time. The mixture was mixed well and shaken at 200 rpm at 25° C. for 40 min.

[0045] Example 5

[0046] (1) 0.2 g of magnetic type A zeolite-based adsorbent was added to 50 mL of wastewater containing 200 mg / L copper ions (pH 5), mixed evenly, and shaken at 150 rpm at 25 °C for 8 h.

[0047] (2) The magnetic type A zeolite that has absorbed the copper ion wastewater is washed three times with anhydrous ethanol and deionized water, and dried in a vacuum drying oven at 70° C. for 7 h to obtain a magnetic type A zeolite-based catalyst loaded with copper ions.

[0048] (3) 0.01 g of a copper-loaded magnetic A-type zeolite-based catalyst was added to 200 mL of wastewater (pH 8) containing 50 mg / L tetracycline, and potassium peroxymonosulfate (3 mmol / L) was added at the same time. The mixture was mixed well and shaken at 180 rpm at 25°C for 1 h.

[0049] The zeolite-based adsorbents used in Examples 1 and 2 were subjected to X-ray diffraction analysis. The results are as follows: Figure 2 As shown. Figure 2 It can be seen that the zeolites used are type A zeolite and magnetic type A zeolite.

[0050] The heavy metal ion adsorption efficiency and adsorption capacity of the zeolite adsorbent used in Examples 1 to 5 were measured. The results are as follows: Figure 3 As shown. It can be seen that the adsorption effects (including adsorption efficiency and adsorption capacity) of different embodiments on heavy metal ions vary with the type of zeolite, the concentration of heavy metal ions, and the volume ratio of the zeolite addition mass to the wastewater containing heavy metal ions. Among them, the adsorption efficiency of Example 1 is the highest, which is 99.87%, and the adsorption capacity of Example 5 is the highest, which is 97.03 mg / g.

[0051] The degradation efficiency of antibiotics was measured on the zeolite-based catalysts used in Examples 1 to 5. The results are as follows: Figure 4As shown. It can be seen that the degradation efficiency of antibiotics in different embodiments is significantly affected by the type of zeolite, the adsorption effect of zeolite on heavy metal ions, the volume ratio of zeolite addition mass to antibiotic-containing wastewater, the type of antibiotics, and the type of oxidant. Among them, the degradation efficiency of Example 2 is the highest, which is 97.86%, and the degradation efficiency of antibiotics in the remaining embodiments is above 50%.

[0052] The parts not mentioned in the above methods can be realized by adopting or drawing on existing technologies.

[0053] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A resource application method of a zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics, characterized in that The following steps are involved: (1) adding zeolite to wastewater containing heavy metal ions, mixing well and then oscillating to adsorb and remove the heavy metal ions in the wastewater; (2) washing, filtering and drying the zeolite adsorbed with heavy metal ions in sequence to obtain a zeolite-based catalyst; (3) A zeolite-based catalyst is added to wastewater containing antibiotics, and an oxidant is added at the same time. The mixture is mixed evenly and then shaken to achieve catalytic degradation of the antibiotics in the wastewater.

2. The resource application method of a zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (1), the zeolite is a natural zeolite or an artificially synthesized magnetic zeolite; the types of zeolites include type A, type X, type Y, type Beta, type ZSM, mordenite and clinoptilolite.

3. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1 is characterized in that: In step (1): the heavy metal ions are one or more of copper, cobalt, nickel, manganese and iron ions.

4. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1 is characterized in that: In step (1), the heavy metal ion concentration in the wastewater is 20-500 mg / L, the pH value of the wastewater is 4-7, and the volume ratio of the zeolite addition mass to the wastewater is 0.5-5:1 g / L.

5. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (1), the oscillation temperature is 10-50° C., the oscillation speed is 50-250 rpm, and the oscillation time is 0.5-24 h.

6. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (2): the washing treatment uses anhydrous ethanol and deionized water in sequence, and the anhydrous ethanol and deionized water are washed 2-3 times respectively; the drying is carried out in a vacuum drying oven, the drying temperature is 60-105°C, and the drying time is 6-12h.

7. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1 is characterized in that: In step (3): the antibiotic is one or more of tetracycline, ofloxacin, tetracycline hydrochloride, and ciprofloxacin.

8. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (3): the concentration of the antibiotic in the wastewater is 5-50 mg / L, the pH value of the wastewater is 4-9, and the volume ratio of the added mass of the zeolite-based catalyst to the wastewater is 0.1-1:1 g / L.

9. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (3), the oxidant is one of potassium peroxymonosulfate, potassium peroxydisulfate or hydrogen peroxide, and the volume ratio of the oxidant addition amount to the wastewater is 0.2-50 mmol / L.

10. The resource application method of the zeolite-based material with secondary synergy of heavy metal adsorption and catalytic degradation of antibiotics according to claim 1, characterized in that: In step (3), the oscillation temperature is 10-50° C., the oscillation speed is 50-250 rpm, and the oscillation time is 5-120 min.

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