Method for preparing environmental function material from modified polyolefin waste plastic

Abstract

The invention belongs to the technical field of environmental pollution control, and discloses a method for preparing an environmental functional material from modified polyolefin waste plastics, and the method comprises the following steps: step 1, carrying out ball milling treatment on treated waste plastic products and mine wastewater; the method comprises the following steps: 1, carrying out mechanical and chemical treatment on mine wastewater by using a ball mill to obtain polyolefin waste plastic containing characteristic groups, 2, filtering and drying the waste plastic subjected to ball milling to obtain a modified polyolefin waste plastic functional material with activated mine wastewater, and 3, detecting water quality parameters of the mine wastewater subjected to mechanical and chemical treatment by using the ball mill, and calculating the removal rate of main ions. Step 4, adding the modified polyolefin waste plastic functional material into the persulfate solution, and then adding the antibiotic into the solution; according to the preparation method, a mode of combining mechanical ball milling of the polyolefin waste plastic and a mine wastewater environment is adopted, the polyolefin waste plastic is activated by utilizing the mine wastewater environment, main ions in the mine wastewater are synchronously removed, and an environment functional material is prepared.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental pollution control, and particularly relates to a method for preparing an environmental functional material from modified polyolefin waste plastics. Background Art

[0002] The world is facing three major crises: climate change, destruction of biodiversity, and pollution problems. Humans must change their relationship with nature. The global environmental pollution problem is becoming increasingly severe. Among them, waste plastic pollution and mine wastewater pollution are two major problems faced by current environmental pollution control. With the acceleration of the industrialization process, the widespread use of plastic products and the increase in mining activities, these two forms of pollution have had a serious impact on the environment and ecosystem. Plastic waste is difficult to degrade and accumulates in the environment for a long time, posing a serious threat to soil, water bodies, and biodiversity. According to a report by the United Nations Environment Programme, plastic pollution causes approximately 9 million premature deaths every year. In addition, microplastics have been widely present in marine organisms and thus affect human health through the food chain. Governments and international organizations are seeking effective technical specifications for waste plastic pollution control to reduce the generation of plastic waste and improve the recycling rate. Mine wastewater pollution is another environmental problem brought about by mining activities. Mine wastewater contains heavy metals and acidic substances, posing a threat to aquatic organisms and human health. According to data from the Ministry of Land and Resources, the annual output of mine wastewater in the country exceeds 11 billion cubic meters, with many pollution risks. The treatment and control of mine wastewater have become an important issue in environmental protection, and effective technical measures and management strategies are needed to reduce wastewater discharge and protect water resources.

[0003] More than 450 million tons of plastics are produced globally every year. Since 1960, a total of 9.6 billion tons of waste plastics have been generated globally, of which polyolefins account for more than 70%. Due to the chemical inertness of the C-C bond in polyolefins, it is more difficult to recycle compared to plastics containing other elements. Currently, the main recycling technologies for polyolefins are landfill incineration and mechanical recycling. These recycling technologies generate greenhouse gases and have low economic benefits. Therefore, how to deal with polyolefin waste plastics has become a research hotspot. In recent years, chemical recycling treatment methods such as pyrolysis, hydrocracking, and oxidative decomposition have been studied to convert waste plastics into oil, gas, or other chemicals to achieve resource reuse. However, due to the stable chemical properties and low reactivity of polyolefin waste plastics, these methods often need to be carried out under high-temperature and high-pressure conditions, and the conversion process is achieved by adding external materials or reagents. This not only increases the requirements for equipment, energy consumption, but also increases the reaction cost, which is not conducive to the popularization and application of conversion technologies.

[0004] Mine wastewater mainly comes from the mining and ore dressing processes, including mine pit water, leaching water from waste rock dumps, ore dressing wastewater, and tailings pond wastewater, etc. These wastewaters are highly acidic and contain various pollutants such as heavy metal ions, sulfate, cyanide, and fluoride, etc. The characteristics of mine wastewater include large water volume, complex composition, great harmfulness, and dispersed drainage outlets that are not concentrated, long flow-through time, and the water quality and quantity are easily affected by seasonal climate. At present, the treatment methods of mine wastewater at home and abroad usually require a large amount of chemical agent dosing, which makes the treatment cost of this kind of wastewater relatively high. Using a cheap way to replace the high-cost chemical agent dosing to achieve the removal of ions in mine wastewater is the development direction of mine wastewater treatment technology. Using waste plastics to replace chemical agents to fix the main ions in mine wastewater can effectively reduce the cost of traditional mine wastewater treatment methods. At the same time, the waste plastics are activated in structure, and the group structures generated by activation endow the waste plastics with new functional characteristics, which have potential application value in the fields of adsorption and catalytic degradation, thus further realizing the resource utilization of waste plastics.

[0005] Therefore, researching and developing the technology for preparing environmental functional materials based on polyolefin waste plastics and mine wastewater is an important method to solve current environmental problems and is crucial for realizing their resource utilization. At present, this method is still in the initial stage of technology at home and abroad, and there is a lack of relevant technologies in this field. How to effectively utilize the metal ions and acidic solution environment in mine wastewater and achieve the treatment and utilization of wastewater are all urgent problems to be solved. When combining polyolefin waste plastics and mine wastewater, the mass transfer and heat transfer problems that are inevitable in the "solid-liquid" system need to be solved in the activation and ion fixation processes.

[0006] Although the team of Zhang Yinlong from Nanjing Forestry University synthesized a new type of photocatalytic material by fixing N-doped TiO2 and graphene oxide (GO) composite materials on a polypropylene (PP) fiber sheet, and the degradation rate of roxithromycin can reach 90%. However, the preparation process of this catalyst is very cumbersome, and the degradation time is long and the degradation rate is low. In addition, due to the chemical stability of waste plastics themselves, there are few active sites during their transformation, resulting in low reaction efficiency. Just using polypropylene plastics as the substrate has little effect in the reaction.

[0007] At present, the treatment methods of mine wastewater are divided into neutralization method, constructed wetland method, microbial method, etc. The method of adding neutralizing agents is easy to operate, but the treatment cost is relatively high; although the biological method has a lower cost, it has higher requirements for water quality, usually requires auxiliary pretreatment, has a long treatment cycle, and it is difficult to achieve large-scale wastewater treatment and disposal. Summary of the Invention

[0008] In the present invention, the persulfate activation process of iron salt has the advantages of low cost, high activation efficiency, and strong oxidation ability. Utilizing the characteristics of high iron ion content and acidic pH in mine wastewater in the southwestern region, the mine wastewater is used as a ball-milling activation aid for waste plastics, and characteristic groups are grafted onto the surface of polyolefin waste plastics. Due to the characteristics of the mine wastewater, this group has the triple effects of activating the intrinsic structure of polyolefin waste plastics, activating persulfate, and adsorbing characteristic ions, thereby promoting the further conversion of polyolefin waste plastics into environmental functional materials. At the same time, during the ball-milling process, the ions in the mine wastewater are fixed to prepare environmental functional materials, and the acidity is reduced, achieving the low-cost purification of mine wastewater, thus achieving the purpose of co-governing mine wastewater and polyolefin waste plastics pollution.

[0009] To achieve the above object, the present invention provides the following technical solution: A method for preparing environmental functional materials from modified polyolefin waste plastics, the method comprising the following steps:

[0010] Step 1: Ball-mill the treated waste plastic products and mine wastewater; after ball-milling, polyolefin waste plastics containing characteristic groups are obtained;

[0011] Step 2: Filter and dry the ball-milled waste plastics to obtain a modified polyolefin waste plastic functional material after activation by mine wastewater;

[0012] Step 3: Detect the water quality parameters of the mine wastewater after ball-milling mechanochemical treatment, and calculate the removal rate of main ions;

[0013] Step 4: Add the modified polyolefin waste plastic functional material into a persulfate solution, and then add antibiotics into the solution; additionally add it into a fluoride-containing solution;

[0014] Step 5: Detect the water quality parameters of the environmental functional material after degrading antibiotics and defluorinating, and calculate the removal rates of antibiotics and defluorination.

[0015] Preferably, in Step 1, the process parameters for ball-milling the treated polyolefin waste plastic products are: ball-milling time 2 - 12 h, ball-milling speed 200 - 600 rpm, diameter of grinding balls 10 mm, number of grinding balls 8 - 16, the dosage ratio of waste plastics to mine wastewater is 1:0.1 - 2.0, and the water quality conditions of the mine wastewater are: iron ion concentration: 10 - 1770 mg / L, aluminum ion concentration: 10 - 970 mg / L, sulfate ion concentration: 800 - 16000 mg / L, that is, the concentration range of main ions.

[0016] Preferably, in Step 2, dry at 70 °C for 12 h.

[0017] Preferably, in Step 3, the dosage ratio of the waste plastics activated by mine wastewater to the persulfate solution is 1:2 - 40.

[0018] Preferably, in step 3, the concentration of the persulfate solution is 4 to 32 g / L; the persulfate solution is one or a combination of two or more of a potassium salt containing peroxymonosulfate, a sodium salt containing peroxymonosulfate, a potassium salt containing persulfate, and a sodium salt containing persulfate.

[0019] Preferably, in step 4, the mixture is transferred to a beaker, and antibiotics and fluoride are degraded at room temperature.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. The present invention adopts a method of combining mechanical ball milling of polyolefin waste plastics with the mine wastewater environment, activates the polyolefin waste plastics by using the mine wastewater environment, synchronously removes the main ions in the mine wastewater, and prepares an environmental functional material.

[0022] 2. The activated polyolefin waste plastic structure formed by the present invention, when applied to the persulfate activation process, its active sites can effectively activate persulfate to generate sulfate radicals and hydroxyl radicals with strong oxidation ability, realizing the dual effects of activating the polyolefin waste plastic structure and activating persulfate, thereby significantly improving the efficiency of degrading antibiotics of the polyolefin waste plastic environmental functional material.

[0023] 3. The method of activating polyolefin waste plastic environmental functional materials with mine wastewater adopted by the present invention can realize the regulation of the activated structure of polyolefin waste plastics by adjusting the ball milling intensity, the addition amount of mine wastewater and the solid-liquid ratio, etc., so as to realize the regulation of the conversion process and efficiency of degrading antibiotics of polyolefin waste plastics, and utilize the metal ions and acidic solution environment in the mine wastewater to realize the reuse of waste. Description of the Drawings

[0024] Figure 1 It is the (a) TC degradation curve and (b) fluoride ion removal curve in Example 1 of the present invention;

[0025] Figure 2 It is the (a) TC degradation curve and (b) fluoride ion removal curve in Example 2 of the present invention;

[0026] Figure 3 It is the (a) TC degradation curve and (b) fluoride ion removal curve in Example 3 of the present invention;

[0027] Figure 4 It is the (a) TC degradation curve and (b) fluoride ion removal curve in Example 4 of the present invention;

[0028] Figure 5 It is the (a) TC degradation curve and (b) fluoride ion removal curve in Example 5 of the present invention;

[0029] Figure 6 For the embodiment 6 of the present invention, (a) TC degradation curve graph, (b) fluoride ion removal curve graph;

[0030] Figure 7 For the embodiment 7 of the present invention, (a) TC degradation curve graph, (b) fluoride ion removal curve graph;

[0031] Figure 8 For the embodiment 8 of the present invention, (a) TC degradation curve graph, (b) fluoride ion removal curve graph;

[0032] Figure 9 For the embodiment 9 of the present invention, (a) TC degradation curve graph, (b) fluoride ion removal curve graph;

[0033] Figure 10 For the embodiment 10 of the present invention, (a) TC degradation curve graph, (b) fluoride ion removal curve graph;

[0034] Figure 11 For the embodiment 11 of the present invention, (a) TC, sulfamethizole, ciprofloxacin degradation curve graphs, (b) fluoride ion removal curve graph. Detailed implementation manners

[0035] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0036] Embodiment 1

[0037] As Figure 1As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a blender and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, ball mill for 4 h at a ball milling speed of 400 rpm. Filter out the ball-milled PP waste sample and place it in an oven, and vacuum dry it for 12 h to obtain an environmental functional material of PP waste plastic activated by mine wastewater. Add 0.05 g of the activated PP waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the environmental functional material of PP waste plastic into 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the concentration of fluoride ions. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of activated polyolefin PP waste plastic to TC reaches 99% in 4 min. The fluoride ion removal rate reaches 95% in 45 min. The concentration of iron ions in the mine wastewater drops to 480 mg / L, and the removal rate reaches 20.0%; the aluminum ion concentration is 303 mg / L, and the removal rate reaches 20.2%; the sulfate ion concentration is 4830 mg / L, and the removal rate reaches 16.3%. TC is tetracycline, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0038] Example 2

[0039] As Figure 2As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a blender and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, ball mill for 4 h at a ball milling speed of 400 rpm. Take out the ball-milled PP waste sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic to 50 mL of 16 g / L sodium persulfate (CAS number: 7775-27-1) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material to 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of activated polyolefin PP waste plastic to TC reaches 99% in 6 min. The fluoride ion removal rate reaches 95% in 55 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0040] Example 3

[0041] As Figure 3As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, ball mill for 4 h at a ball milling speed of 400 rpm. Take out the ball-milled PP waste sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic to 50 mL of pure water, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material to 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, in 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 5% in 10 min. The fluoride ion removal rate reaches 95% in 45 min. TC is tetracycline. The actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0042] Example 4

[0043] As Figure 4As shown, the foamed polyethylene waste, i.e., polyethylene material, PE, is put into a wall breaker and broken up. Take 0.05 g of the PE waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling at a ball milling time of 4 h and a ball milling speed of 400 rpm. Take out the ball-milled PE waste sample and place it in an oven for vacuum drying for 12 h to obtain the PE waste plastic activated by the mine wastewater. Add 0.05 g of PE waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material into 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of the unactivated PE waste plastic, i.e., 0%, 10 min, the degradation rate of the polyolefin PE waste plastic to TC reaches 99% at 5 min. The fluoride ion removal rate reaches 95% at 50 min, TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min, and for defluorination are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0044] Example 5

[0045] As Figure 5As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 15 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling for 4 h at a ball milling speed of 400 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material into 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% at 4.5 min. The fluoride ion removal rate reaches 95% at 48 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0046] Example 6

[0047] As Figure 6As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling for 4 h at a ball milling speed of 600 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material into 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% at 3.5 min. The fluoride ion removal rate reaches 95% at 37 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0048] Example 7

[0049] As Figure 7As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling for 6 h at a ball milling speed of 400 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic to 50 mL of 32 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material to 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, in 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% in 3.5 min. The fluoride ion removal rate reaches 95% in 35 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0050] Example 8

[0051] As Figure 8As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.1 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling at a ball milling time of 4 h and a ball milling speed of 400 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material into 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% in 6 min. The fluoride ion removal rate reaches 95% in 50 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min, and for defluorination are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0052] Example 9

[0053] As Figure 9As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a blender and crushed. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 8 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, and carry out ball milling at a ball milling time of 4 h and a ball milling speed of 400 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain PP waste plastic activated by mine wastewater. Add 0.05 g of PP waste plastic to 50 mL of 16 g / L potassium peroxymonosulfate complex salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material to 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% in 7 min. The fluoride ion removal rate reaches 95% in 60 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0054] Example 10

[0055] As Figure 10As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a blender and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 936 mg / L, aluminum ion concentration: 850 mg / L, sulfate ion concentration: 13530 mg / L, and carry out ball milling for 4 h at a ball milling speed of 400 rpm. Take out the ball-milled waste plastic sample and place it in an oven for vacuum drying for 12 h to obtain mine wastewater-activated PP waste plastic. Add 0.05 g of PP waste plastic to 50 mL of 16 g / L potassium peroxymonosulfate compound salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of 50 ppm tetracycline hydrochloride solution, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to determine the concentration of tetracycline hydrochloride. In addition, add the PP waste plastic environmental functional material to 100 mL of 20 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to determine the fluoride ion concentration. The research results show that, compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, in 10 min, the degradation rate of polyolefin PP waste plastic to TC reaches 99% in 2 min. The fluoride ion removal rate reaches 95% in 20 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0056] Example 11

[0057] As Figure 11As shown, disposable mask waste, i.e., polypropylene material, PP, is put into a wall breaker and broken up. Take 0.05 g of PP waste plastic sample and place it in a ball milling jar, and put 16 grinding balls with a diameter of 10 mm into the jar. Take 5 mL of mine wastewater, including iron ion concentration: 600 mg / L, aluminum ion concentration: 380 mg / L, sulfate ion concentration: 5800 mg / L, ball mill for 4 h at a ball milling speed of 400 rpm. Filter and take out the ball-milled PP waste sample, place it in an oven, and vacuum dry it for 12 h to obtain an environmental functional material of PP waste plastic activated by mine wastewater. Add 0.05 g of the activated PP waste plastic into 50 mL of 16 g / L potassium peroxymonosulfate complex salt (CAS number: 70693-62-8) solution, transfer the mixture to 100 mL of a mixed solution of 50 ppm tetracycline hydrochloride, sulfamethizole, and ciprofloxacin, and stir and react at room temperature for 10 min. Take out 0.1 mL of the degradation solution every 30 s for liquid chromatography to measure the concentration of tetracycline hydrochloride. In addition, add the environmental functional material of PP waste plastic into 100 mL of 5 ppm sodium fluoride solution, stir and react at room temperature for 60 min, and take out 1 mL of the solution every 5 min for ion chromatography to measure the fluoride ion concentration. The research results show that compared with the degradation rate of unactivated PP waste plastic, i.e., 0%, at 10 min, the degradation rate of activated polyolefin PP waste plastic for TC reaches 99% at 4 min, the degradation rate for sulfamethizole reaches 99% at 6 min, and the degradation rate for ciprofloxacin reaches 99% at 5.5 min. The fluoride ion removal rate reaches 95% at 5 min. TC is tetracycline hydrochloride, and the actual sampling times for degrading TC are: 15 s, 30 s, 1 min, 2 min, 4 min, 7 min, and 11 min. For defluorination, they are: 5 min, 10 min, 20 min, 30 min, 45 min, and 60 min.

[0058] In summary, the present invention first proposes a method for preparing a functional material from modified polyolefin waste plastic, and activates the polyolefin waste plastic after being activated by mine wastewater through persulfate activation for antibiotic degradation and defluorination. The generated structural active sites and efficient persulfate activation process can effectively promote the degradation of polyolefin waste plastic against antibiotics. The metal ions exposed by the metal functional groups form ionic bonds with fluoride ions for efficient defluorination, which is conducive to the recycling and resource utilization of polyolefin waste plastic, and at the same time realizes the utilization and treatment of mine wastewater.

[0059] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variation thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0060] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an environmental functional material from modified polyolefin waste plastics, characterized in that: The method includes the following steps: Step 1: Ball-mill the treated waste plastic products and mine wastewater; after ball-milling, polyolefin waste plastics containing characteristic groups are obtained; Step 2: Filter and dry the waste plastics after ball-milling to obtain a modified polyolefin waste plastic functional material activated by mine wastewater; Step 3: Detect the water quality parameters of the mine wastewater after ball-milling mechanochemical treatment and calculate the removal rate of main ions; Step 4: Add the modified polyolefin waste plastic functional material into a persulfate solution, and then add antibiotics into the solution; additionally, add it into a fluoride-containing solution; Step 5: Detect the water quality parameters of the environment functional material after degrading antibiotics and removing fluorine, and calculate the removal rates of antibiotics and fluorine removal.

2. The method for preparing an environmental functional material from a modified polyolefin waste plastic according to claim 1, characterized in that: In Step 1, the process parameters for ball-milling the treated polyolefin waste plastic products are as follows: ball-milling time is 2 - 12 h, ball-milling speed is 200 - 600 rpm, diameter of grinding balls is 10 mm, number of grinding balls is 8 - 16, the dosage ratio of waste plastics to mine wastewater is 1:0.1 - 2.0, and the water quality conditions of mine wastewater are: iron ion concentration: 10 - 1770 mg / L, aluminum ion concentration: 10 - 970 mg / L, sulfate ion concentration: 800 - 16000 mg / L, that is, the concentration range of main ions.

3. A method for preparing an environmental functional material from a modified polyolefin waste plastic according to claim 1, characterized in that: In Step 2, dry at 70 °C for 12 h.

4. A method for preparing an environmental functional material from modified polyolefin waste plastics according to claim 1, characterized in that: In Step 3, the dosage ratio of the waste plastics activated by mine wastewater to the persulfate solution is 1:2 - 40.

5. A method for preparing an environmental functional material from a modified polyolefin waste plastic according to claim 1, characterized in that: In Step 3, the concentration of the persulfate solution is 4 - 32 g / L; among them, the persulfate solution is one or a combination of two or more of potassium salt containing peroxymonosulfate radical, sodium salt containing peroxymonosulfate radical, potassium salt containing persulfate radical, and sodium salt containing persulfate radical.

6. The method for preparing an environmental functional material from a modified polyolefin waste plastic according to claim 1, characterized in that: In Step 4, transfer the mixture to a beaker and degrade antibiotics and remove fluorine at room temperature.

7. Application of a method for co - treating polyolefin waste plastics and mine wastewater, based on the method for preparing an environmental functional material from a modified polyolefin waste plastic according to any one of claims 1 - 6, characterized in that: The described method is applied to the degradation of antibiotics.

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