A harmless treatment device for aluminum electrolysis waste refractory material and application thereof in preparation of asphalt mixture

Abstract

The application provides a harmless treatment device for aluminum electrolysis waste refractory material, which comprises a sodium hydroxide solution bin, an ice acetic acid storage bin, an epichlorohydrin bin, a main body reaction bin and a dodecyl triethoxysilane hydrolysis bin. The application also provides a method for harmless treatment of aluminum electrolysis waste refractory material by using the device and application in preparation of asphalt mixture. The method is that the aluminum electrolysis waste refractory material (SPL) is treated by calcium salt precipitation and then by biomaterial chitosan, then the CT-SPL is crosslinked by epichlorohydrin, and finally the lipophilicity is modified. The method gives SPL stability, excellent adhesion with asphalt, effectively controls the seepage of the toxicity of SPL itself, enables the safe application of SPL in asphalt mixture, and significantly improves the high-temperature stability and water stability of the asphalt mixture, which has significant social and environmental benefits.

Description

Technical Field

[0001] This invention relates to the technical field of highway pavement engineering, specifically to a device for the harmless treatment of waste aluminum electrolysis refractory materials and its application in the preparation of asphalt mixtures. Background Technology

[0002] With my country's rapid economic growth and accelerated urbanization, the highway network is constantly expanding, especially with the development of expressways. Coupled with the massive amount of maintenance and renovation work required for existing expressways, the demand for asphalt concrete remains consistently high. Traditional pavement material preparation and use not only consume large amounts of natural resources but also generate corresponding environmental impacts. Therefore, finding more environmentally friendly and sustainable material solutions while ensuring pavement performance is a pressing issue for the highway construction industry. Meanwhile, the aluminum electrolysis industry, as an important basic raw material industry in my country, generates a huge amount of waste refractory material (SPL) during its production process. How to properly dispose of these wastes containing toxic substances has become an urgent problem to be solved in the fields of environmental protection and resource recycling.

[0003] Waste refractory materials from aluminum electrolysis contain harmful substances such as fluorides, cyanides, and trace amounts of heavy metals. If not properly treated and directly discharged or landfilled, they will cause serious environmental pollution, affecting groundwater quality and soil health, threatening ecological balance and human health. Furthermore, the aluminum electrolysis industry generates a massive amount of waste refractory materials, and as industrial production continues, the accumulation of waste will continue to increase, intensifying the pressure on the environment and resources.

[0004] Against this backdrop, applying aluminum electrolysis waste refractory materials to asphalt pavements has become an innovative attempt. Through scientific and technological means, harmful components in the waste can be effectively reduced, transforming it into a new type of building material with certain value. The processed material can be used as a filler in asphalt mixtures, enhancing the crack resistance and durability of the pavement. This method not only reduces the environmental burden but also decreases dependence on natural resources, achieving resource recycling.

[0005] This invention proposes an apparatus and process for the harmless treatment of waste aluminum electrolysis refractory materials, enabling their safe application in asphalt mixtures. This not only achieves the harmless treatment of waste materials but also improves the pavement performance of the final product. Summary of the Invention

[0006] The purpose of this invention is to provide a device for the harmless treatment of waste refractory materials from aluminum electrolysis, and a method for using this device to harmlessly treat waste refractory materials from aluminum electrolysis and apply them to the preparation of asphalt mixtures.

[0007] The above-mentioned objectives of the present invention are achieved through the following technical solutions:

[0008] This invention provides a harmless treatment device for waste refractory materials from aluminum electrolysis, comprising a sodium hydroxide solution tank, a glacial acetic acid storage tank, an epichlorohydrin tank, a main reaction tank, and a dodecyltriethoxysilane hydrolysis tank. The main reaction tank is equipped with stirring blades and a stirring magnetic coupler, which is mounted on a base inside the main reaction tank and connected to the stirring blades via a connecting rod. A main reaction tank control box is located at the bottom of the main reaction tank. The control box contains a motor, a control operating system, a filter screen, a filter hopper, a centrifugal pump, a drive shaft, and a polytetrafluoroethylene (PTFE) drainage pipe. The motor is connected to the drive shaft. The filter screen is connected to the upper part of the filter hopper, and the centrifugal pump is connected to the lower part of the filter hopper and connected to the PTFE drainage pipe. The sodium hydroxide solution tank, glacial acetic acid storage tank, and epichlorohydrin tank are each connected to an electric three-way reversing valve via PTFE pipes. The PTFE pipeline is connected in sequence to an electric three-way reversing valve and a metering pump, and then to the reaction solution inlet. The dodecyltriethoxysilane hydrolysis chamber is connected to the metering pump via a PTFE pipeline, which in turn is connected to the reaction solution inlet. The top of the main reaction chamber is connected to a hot air furnace via a PTFE hot air delivery pipe. A heating plate, a pH sensor, and a temperature sensor are also installed inside the main reaction chamber. The control system is connected to the heating plate, the hot air furnace, the pH sensor, and the temperature sensor, respectively. The top of the main reaction chamber is covered by a main reaction chamber top panel, which has a solid material feeding port covered by the main reaction chamber top panel, which is connected via a rotating shaft. A deionized water inlet is located near the reaction solution inlet. A reaction chamber discharge port is located at the lower end of the side wall of the main reaction chamber.

[0009] Furthermore, the filter screen has a pore size of 400 mesh and is replaceable.

[0010] Furthermore, the side walls of the main reaction chamber are covered with an insulating outer layer.

[0011] Furthermore, the upper panel of the main reaction chamber and the solid material feeding port are sealed with polytetrafluoroethylene (PTFE) rubber rings; the main reaction chamber and the reaction chamber discharge port are sealed with PTFE rubber rings.

[0012] This invention also provides a method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, comprising using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, and the method comprising the following steps:

[0013] 1) Preparation of oleophilic aluminum electrolytic waste refractory materials:

[0014] ① Add aluminum electrolysis waste refractory powder, calcium hypochlorite solid, and calcium chloride into the main reaction chamber through the solid material feeding port. Add deionized water through the deionized water inlet. The volume of deionized water is 10 times the mass of calcium hypochlorite solid. Start the motor, turn off the heating plate and pH sensor, and use the stirring magnetic coupler to drive the stirring blades to stir. After reacting for more than 48 hours, turn off the motor, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe to obtain wet sample SPL.

[0015] ② Wash the wet SPL obtained in step ① repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, start the hot air heater, motor and temperature sensor, maintain the temperature in the main reaction chamber at 60℃, until the solid sample is dry, and the dried SPL is ready for use;

[0016] ③ By controlling the electric three-way reversing valve, the chitosan acetate solution is introduced from the glacial acetic acid storage chamber into the main reaction chamber. The metering pump determines the volume of the chitosan acetate solution. The chitosan acetate solution reacts with the dried SPL obtained in step ②. The motor, heating plate and temperature sensor are started to control the temperature in the main reaction chamber to 60℃. After stirring for 6 hours, the heating plate is turned off. The electric three-way reversing valve is controlled to introduce sodium hydroxide solution from the sodium hydroxide solution chamber into the main reaction chamber. The speed is controlled at 50 rpm. After stirring for 5 minutes, the centrifugal pump is started to filter out the waste liquid in the main reaction chamber and discharge it through the polytetrafluoroethylene drainage pipe to obtain the wet sample CT-SPL.

[0017] ④ Wash the wet CT-SPL sample obtained in step ③ repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, and the obtained CT-SPL is ready for use.

[0018] ⑤ Epichlorohydrin is introduced from the epichlorohydrin chamber into the main reaction chamber by controlling the electric three-way reversing valve. The volume of epichlorohydrin is determined by the metering pump. Deionized water is added through the deionized water inlet. The epichlorohydrin aqueous solution reacts with the CT-SPL obtained in step ④. The motor, heating plate and temperature sensor are started to control the temperature in the main reaction chamber to 50°C. After stirring for 6 hours, the heating plate is turned off and the centrifugal pump is started to filter out the waste liquid in the main reaction chamber and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain the cross-linked CT-SPL.

[0019] ⑥ Wash the cross-linked CT-SPL obtained in step ⑤ repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, start the hot air heater, motor and temperature sensor, and maintain the temperature in the main reaction chamber at 60℃ until the CT-SPL is dry and ready for use.

[0020] ⑦ By controlling the metering pump, the dodecyltriethoxysilane ethanol aqueous solution is introduced from the dodecyltriethoxysilane hydrolysis chamber into the main reaction chamber. The dodecyltriethoxysilane ethanol aqueous solution reacts with the dried CT-SPL obtained in step ⑥. The motor is started and stirred for 24 hours. Then, the centrifugal pump is started to filter out the waste liquid in the main reaction chamber and discharge it through the polytetrafluoroethylene drainage pipe to obtain the DS-CT-SPL wet sample.

[0021] ⑧ Dry the wet sample DS-CT-SPL obtained in step ⑦, start the hot air furnace, motor and temperature sensor, and maintain the temperature in the main reaction chamber at 60℃ until the solid sample is dry, and obtain the surface oleophilic aluminum electrolytic waste refractory material, which is denoted as DS-CT-SPL. Take out the dried DS-CT-SPL sample through the discharge port of the reaction chamber for later use.

[0022] 2) Take asphalt, coarse and fine aggregates and DS-CT-SPL, place them in an oven at 180℃ and heat for 4 hours. Then take asphalt, DS-CT-SPL and coarse and fine aggregates and place them in an asphalt mixture mixer for mixing. After mixing for 2 minutes, an aluminum electrolysis waste refractory material asphalt mixture is obtained.

[0023] Furthermore, in step ①, the mass ratio of the aluminum electrolysis waste refractory material, calcium hypochlorite, and calcium chloride is 1:2:5; the aluminum electrolysis waste refractory material is obtained by grinding using a vibrating screen, and the aluminum electrolysis waste refractory material simultaneously meets the following requirements: 100% of the material is smaller than 0.6mm, 90-100% is smaller than 0.15mm, and 90-100% is smaller than 0.075mm.

[0024] Furthermore, the mass ratio of dried SPL to chitosan obtained in step ② is 50:1.

[0025] Furthermore, the mass ratio of epichlorohydrin in step ⑤ to CT-SPL obtained in step ④ is 3:100 based on absolute dry weight.

[0026] Furthermore, the volume of dodecyltriethoxysilane in the dodecyltriethoxysilane ethanol aqueous solution is 1% of the total solution volume; the dodecyltriethoxysilane ethanol aqueous solution needs to be hydrolyzed for 48 hours before being added to the main reaction chamber; the ratio of the amount of dried CT-SPL obtained in step ⑥ to the dodecyltriethoxysilane ethanol aqueous solution is 1g:10mL.

[0027] Furthermore, the mass ratio of the asphalt, coarse and fine aggregates, and DS-CT-SPL is 5:96:4; the asphalt is one of road petroleum asphalt No. 70 and SBS modified asphalt; the coarse and fine aggregates are diabase.

[0028] Compared with the prior art, the present invention has the following technical effects:

[0029] (1) This invention uses DS-CT-SPL to replace limestone powder, which can greatly reduce the consumption of high-quality limestone powder, alleviate the problem of mineral resource scarcity, and is beneficial to ecological environmental protection. The surface of the treated DS-CT-SPL material is grafted with dodecyl carbon chain nonpolar functional groups, which exhibits oleophilicity. This solves the problem of good compatibility between aluminum electrolysis waste refractory materials and asphalt molecules, resulting in better adhesion between aluminum electrolysis waste refractory materials and asphalt, and stronger resistance to water peeling. SPL is a hazardous solid waste. According to statistics, my country's annual discharge of aluminum electrolysis waste refractory materials is as high as 1.1 million tons. This invention utilizes SPL to prepare DS-CT-SPL for large-scale application in asphalt concrete, which is beneficial to environmental governance, resource conservation, and turning waste into treasure.

[0030] (2) This invention involves precipitating SPL with calcium salts, then treating it with the biomaterial chitosan, followed by crosslinking CT-SPL with epichlorohydrin, and finally modifying it for lipophilicity. This method endows SPL with stability and excellent adhesion to asphalt, effectively controlling the leaching of SPL's inherent toxicity, enabling its safe application in asphalt mixtures. Simultaneously, it significantly improves the high-temperature stability and water stability of asphalt mixtures, resulting in significant social and environmental benefits.

[0031] (3) This device integrates heating, reaction, and drying functions, achieving integrated harmless treatment of SPL. The integrated design simplifies the processing flow, avoids material transfer between multiple devices, and greatly improves processing efficiency. Since all processing steps are completed within the same device, there is no need to repeatedly heat or cool different devices, thus significantly reducing energy consumption. Compared with traditional processing methods, this device is more energy-efficient and environmentally friendly, helping to reduce carbon emissions and energy waste. Through efficient harmless treatment, this device effectively reduces the pollution of SPL to the environment. The integrated device design makes operation simpler, requiring only one device for maintenance and management, reducing the workload and operational difficulty of operators, while also reducing equipment failure rate and maintenance costs, and improving system reliability. Since the device integrates multiple functions, it does not require multiple separate processing devices, thus greatly reducing the equipment footprint, which is especially important for industrial sites with limited space, enabling more efficient use of limited space resources. By reducing material transfer losses and energy consumption, production costs are reduced, and fines and additional costs due to environmental issues are avoided, improving the overall economic benefits of the enterprise. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the structure of a harmless treatment device for waste refractory materials from aluminum electrolysis according to the present invention.

[0033] Labels in the diagram: 1-Sodium hydroxide solution chamber, 2-Epoxychloropropane chamber, 3-Glacial acetic acid storage chamber, 4-PTFE pipe, 5-Dodecyltriethoxysilane hydrolysis chamber, 6-Metering pump, 7-Hot air furnace, 8-PTFE hot air delivery pipe, 9-Electric three-way reversing valve, 10-Insulation outer layer, 11-Reaction chamber discharge port, 12-PTFE rubber ring, 13-Deionized water inlet, 14-Reaction solution inlet, 15-pH sensor, 16-Temperature sensor, 17-Heating plate, 18-Stirring blade 19-Connecting rod, 20-Stirring magnetic coupler, 21-Drive shaft, 22-Control operating system, 23-Motor, 24-Rotating shaft, 25-Main reaction chamber top panel, 26-Solid material feeding port, 27-Filter screen, 28-Filter hopper, 29-Centrifugal pump, 30-Main reaction chamber control box, 31-Control system display, 32-PTFE drainage pipe, 33-Side of main reaction chamber control box, 34-Main reaction chamber control box base, 35-Main reaction chamber internal base, 36-Main reaction chamber. Detailed Implementation

[0034] like Figure 1As shown, the present invention provides a harmless treatment device for waste refractory materials from aluminum electrolysis, comprising five chambers: a sodium hydroxide solution chamber 1, a glacial acetic acid storage chamber 3, an epichlorohydrin chamber 2, a main reaction chamber 36, and a dodecyltriethoxysilane hydrolysis chamber 5. The main reaction chamber 36 is equipped with stirring blades 18 and a stirring magnetic coupler 20. The stirring magnetic coupler 20 is mounted on a base 35 inside the main reaction chamber and is connected to the stirring blades 18 via a connecting rod 19. A main reaction chamber control box 30 is located at the bottom of the main reaction chamber 36. The reaction chamber control box 30 contains a motor 23, a control operating system 22, a filter screen 27, a filter hopper 28, a centrifugal pump 29, a drive shaft 21, and a polytetrafluoroethylene drainage pipe 3. 2; The motor 23 is connected to the drive shaft 21; the motor 23 drives the drive shaft 21 to rotate, the drive shaft 21 then drives the stirring magnetic coupler 20 to rotate, the stirring magnetic coupler 20 then drives the stirring blades 18 and connecting rod 19 to stir, the drive shaft 21 and the stirring magnetic coupler 20 rotate without contact, and through the magnetic field, they play a role in water isolation; the filter screen 27 is connected to the upper part of the filter hopper 28, the centrifugal pump 29 is connected to the lower part of the filter hopper 28, the centrifugal pump 29 is connected to the polytetrafluoroethylene drainage pipe 32, the filter screen 27, the filter hopper 28 and the centrifugal pump 29 discharge the reaction wastewater through the polytetrafluoroethylene drainage pipe 32; the sodium hydroxide solution tank 1, the glacial acetic acid storage tank 3 and the epichlorohydrin tank 2 are respectively connected to the motor through the polytetrafluoroethylene pipe 4. The three-way reversing valve 9 is connected to the PTFE pipe 4, which is sequentially connected to the electric three-way reversing valve 9 and the metering pump 6, and then connected to the reaction solution inlet 14. The solution is introduced into the main reaction chamber 36 through the reaction solution inlet 14, effectively controlling the type and volume of the solution entering the main reaction chamber 36. The dodecyltriethoxysilane hydrolysis chamber 5 is connected to the metering pump 6 via the PTFE pipe 4. The PTFE pipe 4, connected to the metering pump 6, is then connected to the reaction solution inlet 14, introducing the hydrolysis solution into the main reaction chamber 36 through the reaction solution inlet 14, effectively controlling the volume of the dodecyltriethoxysilane ethanol aqueous solution entering the main reaction chamber 36. The top of the main reaction chamber 36 is connected to the hot air heater 7 via the PTFE hot air delivery pipe 8. Next, the hot air heater 7 sends hot air into the main reaction chamber 36 through the polytetrafluoroethylene hot air delivery pipe 8; the main reaction chamber 36 is also equipped with a heating plate 17, a pH sensor 15 and a temperature sensor 16. The control operating system 22 is connected to the heating plate 17, the hot air heater 7, the pH sensor 15 and the temperature sensor 16 respectively. The values ​​of the pH sensor 15 and the temperature sensor 16 are displayed on the control system display 31 on the control operating system 22; the top of the main reaction chamber 36 is covered by the main reaction chamber upper panel 25. The top of the main reaction chamber 36 has a solid material feeding port 26, which is covered by the main reaction chamber upper panel 25. The main reaction chamber upper panel 25 is connected by a rotating shaft 24.A deionized water inlet 13 is provided near the reaction solution inlet 14; a reaction chamber discharge port 14 is provided at the lower end of the side wall of the main reaction chamber 36.

[0035] Preferably, the filter screen 27 has a pore size of 400 mesh and is replaceable.

[0036] Preferably, the sidewall of the main reaction chamber 36 is covered with an insulating outer layer 10.

[0037] Preferably, the upper panel 25 of the main reaction chamber and the solid material feeding port 26 are sealed by a polytetrafluoroethylene rubber ring 12.

[0038] Preferably, the main reaction chamber 36 and the reaction chamber discharge port 11 are sealed by a polytetrafluoroethylene rubber ring 12.

[0039] Example 1

[0040] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, comprises the following steps:

[0041] 1) Preparation of surface-lipophilic aluminum electrolytic waste refractory material (DS-CT-SPL):

[0042] ① Take 1000g of aluminum electrolysis waste refractory powder (SPL), 2000g of calcium hypochlorite solid, and 5000g of calcium chloride and add them into the main reaction chamber 36 through the solid material feeding port 26. Add 20000mL of deionized water through the deionized water inlet 13. Start the motor 23, turn off the heating plate 17 and pH sensor 15, and use the stirring magnetic coupler 20 to drive the stirring blades 18 to stir. After reacting for more than 48 hours, stop the motor 23 and start the centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32. The SPL powder is obtained by grinding with a vibrating screen. The particle size of the SPL powder simultaneously meets the following requirements: 100% of the particles are less than 0.6mm, 90-100% are less than 0.15mm, and 90-100% are less than 0.075mm.

[0043] ② Wash the wet SPL obtained in step ① repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 6, start the hot air heater 7, motor 23 and temperature sensor 16, maintain the temperature in the main reaction chamber 36 at 60℃ until the solid sample is dry, and the dried SPL is ready for use.

[0044] ③ By controlling the electric three-way reversing valve 9 and the metering pump 6, 5000 mL of chitosan acetate solution is introduced from the glacial acetic acid storage chamber 3 into the main reaction chamber 36. The chitosan acetate solution reacts with the dried SPL obtained in step ②. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature in the main reaction chamber 36 to 60℃. After stirring for 6 hours, the heating plate 17 is turned off, and the electric three-way reversing valve 9 is controlled to introduce sodium hydroxide solution (2 mol / L) from the sodium hydroxide solution chamber 1 into the main reaction chamber 36. The speed is controlled at 50 rpm. After stirring for 5 minutes, the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain wet sample CT-SPL. The volume concentration of the acetic acid solution used in preparing the chitosan acetate solution is 5%. The mass ratio of dried SPL obtained in step ② to chitosan is 50:1.

[0045] ④ Wash the wet CT-SPL sample obtained in step ③ repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 6, and the obtained CT-SPL is ready for use.

[0046] ⑤ By controlling the electric three-way reversing valve 9 and the metering pump 6, 25.4 mL of epichlorohydrin is introduced from the epichlorohydrin chamber 2 into the main reaction chamber 36. 3000 mL of deionized water is added through the deionized water inlet 13. The epichlorohydrin aqueous solution reacts with the CT-SPL obtained in step ④. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature in the main reaction chamber 36 to 50℃. After stirring for 6 hours, the heating plate 17 is turned off and the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain the cross-linked CT-SPL. The mass ratio of epichlorohydrin to the CT-SPL obtained in step ④ is 3:100 based on the oven-dry weight.

[0047] ⑥ Wash the cross-linked CT-SPL obtained in step ⑤ repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 6, start the hot air heater 7, motor 23 and temperature sensor 16 to maintain the temperature in the main reaction chamber 36 at 60°C until the CT-SPL is dry and ready for use.

[0048] ⑦ By controlling the metering pump 6, 10000 mL of dodecyltriethoxysilane ethanol aqueous solution is introduced from the dodecyltriethoxysilane hydrolysis chamber 5 into the main reaction chamber 36. The dodecyltriethoxysilane ethanol aqueous solution reacts with the dried CT-SPL obtained in step ⑥. The motor 23 is started, and after stirring for 24 hours, the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain the DS-CT-SPL wet sample. When preparing the dodecyltriethoxysilane ethanol aqueous solution, an ethanol aqueous solution with a ratio of V (anhydrous ethanol):V (deionized water) = 4:1 is used. The volume of dodecyltriethoxysilane in the dodecyltriethoxysilane ethanol aqueous solution is 1% of the total volume of the solution. The dodecyltriethoxysilane ethanol aqueous solution needs to be hydrolyzed for 48 hours before being added to the main reaction chamber 36. The ratio of dried CT-SPL obtained in step ⑥ to the dodecyltriethoxysilane ethanol aqueous solution is 1 g: 10 mL.

[0049] ⑧ Dry the wet sample DS-CT-SPL obtained in step ⑦, start the hot air heater 7, motor 23 and temperature sensor 16, and maintain the temperature in the main reaction chamber 36 at 60°C until the solid sample is dry, and obtain the surface oleophilic aluminum electrolytic waste refractory material, which is denoted as DS-CT-SPL. Take out the dried DS-CT-SPL sample through the discharge port 11 of the reaction chamber for later use.

[0050] 2) Weigh out road petroleum asphalt No. 70, diabase and DS-CT-SPL in a mass ratio of 5:96:4, heat them in an oven at 180℃ for 4 hours, then put road petroleum asphalt No. 70, diabase and DS-CT-SPL into an asphalt mixture mixer and mix them. After mixing for 2 minutes, an aluminum electrolysis waste refractory material asphalt mixture is obtained.

[0051] Example 2

[0052] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, comprises the following steps:

[0053] 1) Preparation of surface-lipophilic aluminum electrolytic waste refractory material (DS-CT-SPL):

[0054] ① Take 1000g of aluminum electrolysis waste refractory powder (SPL), 2000g of calcium hypochlorite solid, and 5000g of calcium chloride and add them into the main reaction chamber 36 through the solid material feeding port 26. Add 20000mL of deionized water through the deionized water inlet 13. Start the motor 23, turn off the heating plate 17 and pH sensor 15, and use the stirring magnetic coupler 20 to drive the stirring blades 18 to stir. After reacting for more than 48 hours, stop the motor 23 and start the centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32. The SPL powder is obtained by grinding with a vibrating screen. The particle size of the SPL powder simultaneously meets the following requirements: 100% of the particles are less than 0.6mm, 90-100% are less than 0.15mm, and 90-100% are less than 0.075mm.

[0055] ② Wash the wet SPL obtained in step ① repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 7, start the hot air heater 7, motor 23 and temperature sensor 16, maintain the temperature in the main reaction chamber 36 at 60℃, until the solid sample is dry, and the dried SPL is ready for use.

[0056] ③ By controlling the electric three-way reversing valve 9 and the metering pump 6, 5000 mL of chitosan acetate solution is introduced from the glacial acetic acid storage chamber 3 into the main reaction chamber 36. The chitosan acetate solution reacts with the dried SPL obtained in step ②. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature in the main reaction chamber 36 to 60℃. After stirring for 6 hours, the heating plate 17 is turned off, and the electric three-way reversing valve 9 is controlled to introduce sodium hydroxide solution (2 mol / L) from the sodium hydroxide solution chamber 1 into the main reaction chamber 36. The speed is controlled at 50 rpm. After stirring for 5 minutes, the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain wet sample CT-SPL. The volume concentration of the acetic acid solution used in preparing the chitosan acetate solution is 5%. The mass ratio of dried SPL obtained in step ② to oven-dried chitosan is 50:1.

[0057] ④ Wash the wet CT-SPL sample obtained in step ③ repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 7, and the obtained CT-SPL is ready for use.

[0058] ⑤ By controlling the electric three-way reversing valve 9 and the metering pump 6, 25.4 mL of epichlorohydrin is introduced from the epichlorohydrin chamber 2 into the main reaction chamber 36. 3000 mL of deionized water is added through the deionized water inlet 13. The epichlorohydrin aqueous solution reacts with the CT-SPL obtained in step ④. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature of the main reaction chamber 36 to 50℃. After stirring for 6 hours, the heating plate 17 is turned off and the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain the cross-linked CT-SPL. The mass ratio of epichlorohydrin to the CT-SPL obtained in step ④ is 3:100 based on the oven-dry weight.

[0059] ⑥ Repeatedly wash the cross-linked CT-SPL obtained in step ⑤, add deionized water through deionized water inlet 13 until the water level covers the solid sample, start pH sensor 15 and motor 23, turn off heating plate 17, stir for 15 minutes, start centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36, and discharge it through polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 7, start hot air heater 7, motor 23 and temperature sensor 16 to maintain the temperature in the main reaction chamber 36 at 60℃ until the CT-SPL is dry and ready for use.

[0060] ⑦ 10000 mL of dodecyltriethoxysilane ethanol aqueous solution was introduced from the dodecyltriethoxysilane hydrolysis chamber 5 into the main reaction chamber 36 via metering pump 6. The dodecyltriethoxysilane ethanol aqueous solution reacted with the dried CT-SPL obtained in step ⑥. After stirring for 24 hours with motor 23, centrifugal pump 29 was started to filter out the waste liquid in the main reaction chamber 36 and discharge it through polytetrafluoroethylene drainage pipe 32 to obtain a wet DS-CT-SPL sample. The dodecyltriethoxysilane ethanol aqueous solution used in the preparation of the dodecyltriethoxysilane aqueous solution was an ethanol-water solution with a ratio of V(anhydrous ethanol):V(deionized water) = 4:1; the volume of dodecyltriethoxysilane in the dodecyltriethoxysilane ethanol aqueous solution was 1% of the total solution volume; the dodecyltriethoxysilane ethanol aqueous solution needed to be hydrolyzed for 48 hours before being added to the main reaction chamber 36; the ratio of dried CT-SPL obtained in step ⑥ to the dodecyltriethoxysilane ethanol aqueous solution was 1 g: 10 mL.

[0061] ⑧ Dry the wet sample DS-CT-SPL obtained in step ⑦, start the hot air heater 7, motor 23 and temperature sensor 16, and maintain the temperature in the main reaction chamber 36 at 60°C until the solid sample is dry, and obtain the surface oleophilic aluminum electrolytic waste refractory material, which is denoted as DS-CT-SPL. Take out the dried DS-CT-SPL sample through the discharge port 11 of the reaction chamber for later use.

[0062] 2) The preparation of the aluminum electrolysis waste refractory asphalt mixture is the same as in Example 1.

[0063] Example 3

[0064] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, comprises the following steps:

[0065] 1) Preparation of surface-lipophilic aluminum electrolytic waste refractory material (DS-CT-SPL):

[0066] ① Take 1000g of aluminum electrolysis waste refractory powder (SPL), 2000g of calcium hypochlorite solid, and 5000g of calcium chloride and add them into the main reaction chamber 36 through the solid material feeding port 26. Add 20000mL of deionized water through the deionized water inlet 13. Start the motor 23, turn off the heating plate 17 and pH sensor 15, and use the stirring magnetic coupler 20 to drive the stirring blades 18 to stir. After reacting for more than 48 hours, stop the motor 23 and start the centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32. The SPL powder is obtained by grinding with a vibrating screen. The particle size of the SPL powder simultaneously meets the following requirements: 100% of the particles are less than 0.6mm, 90-100% are less than 0.15mm, and 90-100% are less than 0.075mm.

[0067] ② Wash the wet SPL obtained in step ① repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 8, start the hot air heater 7, motor 23 and temperature sensor 16, maintain the temperature in the main reaction chamber 36 at 60℃ until the solid sample is dry, and the dried SPL is ready for use.

[0068] ③ By controlling the electric three-way reversing valve 9 and the metering pump 6, 5000 mL of chitosan acetate solution is introduced from the glacial acetic acid storage chamber 3 into the main reaction chamber 36. The chitosan acetate solution reacts with the dried SPL obtained in step ②. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature of the main reaction chamber 36 at 60℃. After stirring for 6 hours, the heating plate 17 is turned off, and the electric three-way reversing valve 9 is controlled to introduce sodium hydroxide solution (2 mol / L) from the sodium hydroxide solution chamber 1 into the main reaction chamber 36. The speed is controlled at 50 rpm. After stirring for 5 minutes, the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain wet sample CT-SPL. The volume concentration of the acetic acid solution used in preparing the chitosan acetate solution is 5%. The mass ratio of dried SPL obtained in step ② to oven-dried chitosan is 50:1.

[0069] ④ Wash the wet CT-SPL sample obtained in step ③ repeatedly, add deionized water through the deionized water inlet 13 until the water level covers the solid sample, start the pH sensor 15 and motor 23, turn off the heating plate 17, stir for 15 minutes, start the centrifugal pump 29, filter out the waste liquid in the main reaction chamber 36, and discharge it through the polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 8, and the obtained CT-SPL is ready for use.

[0070] ⑤ By controlling the electric three-way reversing valve 9 and the metering pump 6, 25.4 mL of epichlorohydrin is introduced from the epichlorohydrin chamber 2 into the main reaction chamber 36. 3000 mL of deionized water is added through the deionized water inlet 13. The epichlorohydrin aqueous solution reacts with the CT-SPL obtained in step ④. The motor 23, heating plate 17 and temperature sensor 16 are started to control the temperature of the main reaction chamber 36 to 50℃. After stirring for 6 hours, the heating plate 17 is turned off and the centrifugal pump 29 is started to filter out the waste liquid in the main reaction chamber 36 and discharge it through the polytetrafluoroethylene drainage pipe 32 to obtain the cross-linked CT-SPL. The mass ratio of epichlorohydrin to the CT-SPL obtained in step ④ is 3:100 based on the oven-dry weight.

[0071] ⑥ Repeatedly wash the cross-linked CT-SPL obtained in step ⑤, add deionized water through deionized water inlet 13 until the water level covers the solid sample, start pH sensor 15 and motor 23, turn off heating plate 17, stir for 15 minutes, start centrifugal pump 29 to filter out the waste liquid in the main reaction chamber 36, and discharge it through polytetrafluoroethylene drainage pipe 32. Repeat the operation until the solution pH is 8, start hot air heater 7, motor 23 and temperature sensor 16 to maintain the temperature in the main reaction chamber 36 at 60℃ until the CT-SPL is dry and ready for use.

[0072] ⑦ 10000 mL of dodecyltriethoxysilane ethanol aqueous solution was introduced from the dodecyltriethoxysilane hydrolysis chamber 5 into the main reaction chamber 36 via metering pump 6. The dodecyltriethoxysilane ethanol aqueous solution reacted with the dried CT-SPL obtained in step ⑥. After stirring for 24 hours with motor 23, centrifugal pump 29 was started to filter out the waste liquid in the main reaction chamber 36 and discharge it through polytetrafluoroethylene drainage pipe 32 to obtain a wet DS-CT-SPL sample. The dodecyltriethoxysilane ethanol aqueous solution used in the preparation of the dodecyltriethoxysilane aqueous solution was an ethanol-water solution with a ratio of V(anhydrous ethanol):V(deionized water) = 4:1; the volume of dodecyltriethoxysilane in the dodecyltriethoxysilane ethanol aqueous solution was 1% of the total solution volume; the dodecyltriethoxysilane ethanol aqueous solution needed to be hydrolyzed for 48 hours before being added to the main reaction chamber 36; the ratio of dried CT-SPL obtained in step ⑥ to the dodecyltriethoxysilane ethanol aqueous solution was 1 g: 10 mL.

[0073] ⑧ Dry the wet sample DS-CT-SPL obtained in step ⑦, start the hot air heater 7, motor 23 and temperature sensor 16, and maintain the temperature in the main reaction chamber 36 at 60°C until the solid sample is dry, and obtain the surface oleophilic aluminum electrolytic waste refractory material, which is denoted as DS-CT-SPL. Take out the dried DS-CT-SPL sample through the discharge port 11 of the reaction chamber for later use.

[0074] 2) The preparation of the aluminum electrolysis waste refractory asphalt mixture is the same as in Example 1.

[0075] Example 4

[0076] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, comprises the following steps:

[0077] 1) The preparation of the surface oleophilic aluminum electrolytic waste refractory material (DS-CT-SPL) is the same as in Example 1;

[0078] 2) Weigh SBS modified asphalt, diabase and DS-CT-SPL in a mass ratio of 5:96:4, heat them in an oven at 180℃ for 4 hours, and then mix them in an asphalt mixture mixer for 2 minutes to obtain an aluminum electrolysis waste refractory material asphalt mixture.

[0079] Example 5

[0080] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, using the aforementioned harmless treatment device for waste refractory materials from aluminum electrolysis, comprises the following steps:

[0081] 1) The preparation of the surface oleophilic aluminum electrolytic waste refractory material (DS-CT-SPL) is the same as in Example 2;

[0082] 2) The preparation of the asphalt mixture of aluminum electrolysis waste refractory materials is the same as in Example 4.

[0083] Example 6

[0084] A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, comprising the following steps:

[0085] 1) The preparation of the surface oleophilic aluminum electrolytic waste refractory material (DS-CT-SPL) is the same as in Example 3;

[0086] 2) The preparation of the asphalt mixture of aluminum electrolysis waste refractory materials is the same as in Example 4.

[0087] Comparative Example 1:

[0088] Replace DS-CT-SPL with limestone powder in the same proportion. Other materials and preparation processes are as follows:

[0089] Road petroleum asphalt No. 70, diabase and limestone powder are weighed in a mass ratio of 5:96:4, heated in an oven at 180℃ for 4 hours, and then mixed in an asphalt mixture mixer for 2 minutes to obtain asphalt mixture.

[0090] Comparative Example 2:

[0091] Replace DS-CT-SPL with limestone powder in the same proportion. Other materials and preparation processes are as follows:

[0092] Weigh SBS modified asphalt, diabase, and limestone powder in a mass ratio of 5:96:4, heat them in an oven at 180℃ for 4 hours, and then mix them in an asphalt mixture mixer for 2 minutes to obtain the asphalt mixture.

[0093] The asphalt mixtures prepared by the above method were subjected to performance tests according to the current domestic standards "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTGE20-2011) and "Leaching Methods for Solid Waste: Horizontal Oscillation Method" (HJ557-2010).

[0094] Test items:

[0095]

[0096]

[0097] Standard rutting tests, immersion Marshall tests, and freeze-thaw splitting tests were all conducted according to the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTGE20-2011). To further verify the effect of DS-CT-SPL on improving the high-temperature performance of asphalt concrete, and considering the long-term hot and humid climate conditions in southern regions, high-temperature rutting tests were conducted on the asphalt mixture while maintaining the test wheel contact pressure at 0.7 MPa, based on the already conducted standard rutting tests. Simultaneously, considering the increasing number of vehicles in my country, the continuous development of the transportation industry, and the increasing average load weight of freight vehicles, even to the point of overloading, heavy-load rutting tests were conducted on the asphalt mixture while maintaining the test temperature at 60℃, and increasing the test wheel contact pressure from 0.7 MPa to 1.0 MPa, based on the already conducted standard rutting tests.

[0098] The fluoride leaching test of asphalt mixture was conducted according to the "Leaching Method of Solid Waste Leaching - Horizontal Oscillation Method" (HJ557-2010), and the concentration of fluoride ions in the leachate was tested according to the method of "Identification Standard for Hazardous Waste - Identification of Toxic Substance Content" (GB5085.6-2007).

[0099] In addition, to further verify the effect of DS-CT-SPL on improving the water stability of asphalt concrete, a water immersion rutting test was conducted based on the standard rutting test. Maintaining a constant test temperature of 60℃ and a test wheel contact pressure of 0.7MPa, the molded rutting specimens, which had been left at room temperature for 48 hours, were placed together with the mold in a stainless steel high-temperature resistant basin. Sufficient water at 60℃ was poured in to completely submerge the specimens and molds. The basin containing the specimens and 60℃ water was then transferred to an oven set at 60℃ for 5 hours. Following this, rutting tests were conducted to investigate the effect of DS-CT-SPL on the rutting resistance of asphalt concrete under water immersion conditions.

[0100] The test results are as follows:

[0101] I. High-Temperature Stability Study:

[0102]

[0103]

[0104] The test results and comparison results show that, due to the addition of DS-CT-SPL, the standard dynamic stability of the base asphalt mixture reached a maximum of 6062 cycles / mm, and the standard dynamic stability of the SBS asphalt mixture reached a maximum of 7721 cycles / mm. This can enhance the rutting resistance of asphalt mixtures and, to a certain extent, improve and maintain the ability of asphalt mixtures to resist rutting.

[0105] II. Water stability study:

[0106] (a) Immersion Marshall test:

[0107] Experimental Project Standard stability (kN) Standard flow rate (mm) Water immersion stability (kN) Residual stability (%) Example 1 12.54 4.46 11.32 90.27 Example 2 12.89 4.22 11.22 87.04 Example 3 11.45 4.97 10.21 89.17 Comparative Example 1 9.98 5.36 8.07 80.86 Example 4 15.13 4.09 13.88 91.74 Example 5 14.06 4.26 12.68 90.18 Example 6 16.13 3.91 14.60 90.51 Comparative Example 2 10.6 5.46 8.87 83.68

[0108] The test results and comparison results show that, due to the addition of DS-CT-SPL, the water immersion residual stability of the matrix asphalt mixture reached a maximum of 90.27%, and that of the SBS asphalt mixture reached a maximum of 91.74%. Compared with mineral filler, DS-CT-SPL can effectively improve the water stability of asphalt mixtures.

[0109] (II) Freeze-thaw splitting test:

[0110]

[0111]

[0112] The test results and comparison results show that, due to the addition of DS-CT-SPL, the freeze-thaw splitting tensile strength ratio of the matrix asphalt mixture reached a maximum of 88.41%, and the freeze-thaw splitting tensile strength ratio of the SBS asphalt mixture reached a maximum of 91.62%. Compared with mineral filler, DS-CT-SPL improves and maintains the water stability performance of asphalt mixture to a certain extent.

[0113] (III) Immersion Rutting Test:

[0114] Experimental Project Immersion dynamic stability (cycles / mm) Example 1 3399 Example 2 3264 Example 3 3044 Comparative Example 1 2449 Example 4 4174 Example 5 3990 Example 6 4413 Comparative Example 2 3322

[0115] The test results and comparison results show that, due to the addition of DS-CT-SPL, the dynamic stability of the base asphalt mixture under water immersion increased to a maximum of 3399 cycles / mm, and the dynamic stability of the SBS asphalt mixture under water immersion increased to a maximum of 4413 cycles / mm. Compared with mineral powder filler, this indicates that the addition of DS-CT-SPL can also improve and maintain the asphalt mixture's ability to resist rutting to a certain extent, as well as its ability to resist water damage to a certain extent.

[0116] (v) Fluoride ion leaching test

[0117] Experimental Project Fluoride ion concentration in leachate (mg / L) Example 1 1.76 Example 2 1.41 Example 3 1.58 Example 4 0.99 Example 5 0.91 Example 6 1.34

[0118] The test results and comparison results show that the highest fluoride ion leachate of asphalt mixture is only 1.76 mg / L (<100 mg / L), which is far less than the requirements of the standard (GB5085.6-2007). After surface oleophilic modification treatment, SPL can be better compatible with asphalt. The asphalt molecules block the water molecules and the inorganic fluorides in SPL, effectively reducing the ionization of inorganic fluorides in water and effectively inhibiting the leaching of fluoride ions.

Claims

1. A device for the harmless treatment of waste refractory materials from aluminum electrolysis, characterized in that: The system includes a sodium hydroxide solution chamber, a glacial acetic acid storage chamber, an epichlorohydrin chamber, a main reaction chamber, and a dodecyltriethoxysilane hydrolysis chamber. The main reaction chamber is equipped with stirring blades and a magnetic stirring coupler. The magnetic stirring coupler is mounted on a base inside the main reaction chamber and connected to the stirring blades via a connecting rod. A control box is located at the bottom of the main reaction chamber. The control box contains a motor, a control operating system, a filter screen, a filter hopper, a centrifugal pump, a drive shaft, and a PTFE drainage pipe. The motor is connected to the drive shaft. The filter screen is connected to the upper part of the filter hopper, and the centrifugal pump is connected to the lower part of the filter hopper and connected to the PTFE drainage pipe. The sodium hydroxide solution chamber, glacial acetic acid storage chamber, and epichlorohydrin chamber are each connected to an electric three-way reversing valve via PTFE pipes. The PTFE pipes are sequentially connected to an electric three-way reversing valve. The three-way reversing valve and metering pump are connected to the reaction solution inlet; the dodecyltriethoxysilane hydrolysis chamber is connected to the metering pump via a PTFE pipe, which in turn connects to the reaction solution inlet; the top of the main reaction chamber is connected to the hot air furnace via a PTFE hot air delivery pipe; a heating plate, pH sensor, and temperature sensor are also installed inside the main reaction chamber, and the control system is connected to the heating plate, hot air furnace, pH sensor, and temperature sensor respectively; the top of the main reaction chamber is covered by a main reaction chamber top panel, and a solid material feeding port is opened on the top of the main reaction chamber, which is covered by the main reaction chamber top panel, which is connected via a rotating shaft; a deionized water inlet is opened near the reaction solution inlet; and a reaction chamber discharge port is opened at the lower end of the side wall of the main reaction chamber.

2. The device for harmless treatment of waste refractory materials from aluminum electrolysis according to claim 1, characterized in that: The filter screen has a pore size of 400 mesh and is replaceable.

3. The device for harmless treatment of waste refractory materials from aluminum electrolysis according to claim 1, characterized in that: The side walls of the main reaction chamber are covered with an insulating outer layer.

4. The device for harmless treatment of waste refractory materials from aluminum electrolysis according to claim 1, characterized in that: The main reaction chamber's upper panel and solid material feeding port are sealed with PTFE rubber rings; the main reaction chamber and the reaction chamber discharge port are sealed with PTFE rubber rings.

5. A method for the harmless treatment of waste refractory materials from aluminum electrolysis and their application in the preparation of asphalt mixtures, characterized in that, The method includes a harmless treatment apparatus for waste refractory materials from aluminum electrolysis as described in any one of claims 1 to 4, comprising the following steps: 1) Preparation of oleophilic aluminum electrolytic waste refractory materials: ① Add aluminum electrolysis waste refractory powder, calcium hypochlorite solid, and calcium chloride into the main reaction chamber through the solid material feeding port. Add deionized water through the deionized water inlet. The volume of deionized water is 10 times the mass of calcium hypochlorite solid. Start the motor, turn off the heating plate and pH sensor, and use the stirring magnetic coupler to drive the stirring blades to stir. After reacting for more than 48 hours, turn off the motor, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe to obtain wet sample SPL. ② Wash the wet SPL obtained in step ① repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, start the hot air heater, motor and temperature sensor, maintain the temperature in the main reaction chamber at 60℃, until the solid sample is dry, and the dried SPL is ready for use; ③ By controlling the electric three-way reversing valve, the chitosan acetate solution is introduced from the glacial acetic acid storage chamber into the main reaction chamber. The metering pump determines the volume of the chitosan acetate solution. The chitosan acetate solution reacts with the dried SPL obtained in step ②. The motor, heating plate and temperature sensor are started to control the temperature in the main reaction chamber to 60℃. After stirring for 6 hours, the heating plate is turned off. The electric three-way reversing valve is controlled to introduce sodium hydroxide solution from the sodium hydroxide solution chamber into the main reaction chamber. The speed is controlled at 50 rpm. After stirring for 5 minutes, the centrifugal pump is started to filter out the waste liquid in the main reaction chamber and discharge it through the polytetrafluoroethylene drainage pipe to obtain the wet sample CT-SPL. ④ Wash the wet CT-SPL sample obtained in step ③ repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, and the obtained CT-SPL is ready for use. ⑤ By controlling the electric three-way reversing valve, epichlorohydrin is introduced from the epichlorohydrin chamber into the main reaction chamber. The metering pump determines the volume of epichlorohydrin. Deionized water is added through the deionized water inlet. The epichlorohydrin aqueous solution reacts with the CT-SPL obtained in step ④. The motor, heating plate and temperature sensor are started to control the temperature in the main reaction chamber to 50°C. After stirring for 6 hours, the heating plate is turned off and the centrifugal pump is started to filter out the waste liquid in the main reaction chamber. The waste liquid is discharged through the polytetrafluoroethylene drainage pipe (32) to obtain the cross-linked CT-SPL. ⑥ Wash the cross-linked CT-SPL obtained in step ⑤ repeatedly, add deionized water through the deionized water inlet until the water level covers the solid sample, start the pH sensor and motor, turn off the heating plate, stir for 15 minutes, start the centrifugal pump, filter out the waste liquid in the main reaction chamber, and discharge it through the polytetrafluoroethylene drainage pipe. Repeat the operation until the solution pH is 6-8, start the hot air heater, motor and temperature sensor, and maintain the temperature in the main reaction chamber at 60℃ until the CT-SPL is dry and ready for use. ⑦ By controlling the metering pump, the dodecyltriethoxysilane ethanol aqueous solution is introduced from the dodecyltriethoxysilane hydrolysis chamber into the main reaction chamber. The dodecyltriethoxysilane ethanol aqueous solution reacts with the dried CT-SPL obtained in step ⑥. The motor is started and stirred for 24 hours. Then, the centrifugal pump is started to filter out the waste liquid in the main reaction chamber and discharge it through the polytetrafluoroethylene drainage pipe to obtain the DS-CT-SPL wet sample. ⑧ Dry the wet sample DS-CT-SPL obtained in step ⑦, start the hot air furnace, motor and temperature sensor, and maintain the temperature in the main reaction chamber at 60℃ until the solid sample is dry, and obtain the surface oleophilic aluminum electrolytic waste refractory material, which is denoted as DS-CT-SPL. Take out the dried DS-CT-SPL sample through the discharge port of the reaction chamber for later use. 2) Take asphalt, coarse and fine aggregates and DS-CT-SPL, put them in an oven at 180℃ and heat for 4 hours. Then put the asphalt, DS-CT-SPL and coarse and fine aggregates into an asphalt mixture mixer and mix for 2 minutes to obtain an aluminum electrolysis waste refractory material asphalt mixture.

6. The method for harmlessly treating aluminum electrolysis waste refractory materials and applying them to the preparation of asphalt mixtures according to claim 5, characterized in that, In step ①, the mass ratio of aluminum electrolysis waste refractory material, calcium hypochlorite, and calcium chloride is 1:2:

5. The aluminum electrolysis waste refractory material is obtained by grinding using a vibrating screen. The aluminum electrolysis waste refractory material simultaneously meets the following requirements: 100% of the material is smaller than 0.6mm, 90-100% is smaller than 0.15mm, and 90-100% is smaller than 0.075mm.

7. The method for harmlessly treating aluminum electrolysis waste refractory materials and applying them to the preparation of asphalt mixtures according to claim 5, characterized in that, The mass ratio of dried SPL to chitosan obtained in step ② is 50:

1.

8. The method for harmlessly treating aluminum electrolysis waste refractory materials and applying them to the preparation of asphalt mixtures according to claim 5, characterized in that, The mass ratio of epichlorohydrin in step ⑤ to CT-SPL obtained in step ④ is 3:100 based on absolute dry weight.

9. The method for harmlessly treating aluminum electrolysis waste refractory materials and applying them to the preparation of asphalt mixtures according to claim 5, characterized in that, The volume of dodecyltriethoxysilane in the dodecyltriethoxysilane ethanol aqueous solution is 1% of the total solution volume; the dodecyltriethoxysilane ethanol aqueous solution needs to be hydrolyzed for 48 hours before being added to the main reaction chamber; the ratio of the amount of dried CT-SPL obtained in step ⑥ to the dodecyltriethoxysilane ethanol aqueous solution is 1g:10mL.

10. The method for harmlessly treating aluminum electrolysis waste refractory materials and applying them to the preparation of asphalt mixtures according to claim 5, characterized in that, The mass ratio of asphalt, coarse and fine aggregates, and DS-CT-SPL is 5:96:4; the asphalt is one of road petroleum asphalt No. 70 and SBS modified asphalt; the coarse and fine aggregates are diabase.

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