Method for preparing emulsified asphalt based on waste tire pyrolysis oil storage tank water cutting

Abstract

The present application relates to the technical field of waste tire pyrolysis oil storage tank water cutting resource utilization, in particular to a method for preparing emulsified asphalt based on waste tire pyrolysis oil storage tank water cutting; the method for preparing emulsified asphalt based on waste tire pyrolysis oil storage tank water cutting comprises the following steps: S1, water cutting pretreatment; S2, preparing emulsified asphalt: S2-1, soap solution preparation, S2-2, asphalt preparation, S2-3, colloid mill emulsification; the present application fully utilizes the waste tire pyrolysis oil storage tank water cutting resource, replaces clean water to prepare emulsified asphalt, and uses mild Fenton technology to convert the dissolved aromatic and heterocyclic compounds in the water cutting into endogenous free radical trapping agents and ultraviolet absorbers, realizes zero discharge of hazardous waste and "waste treatment with waste", and significantly reduces the production cost and environmental protection disposal pressure.

Description

Technical Field

[0001] This invention relates to the field of water-based resource utilization technology for waste tire pyrolysis oil storage tanks, specifically to a method for preparing emulsified asphalt based on water-based water removal from waste tire pyrolysis oil storage tanks. Background Technology

[0002] When oil products from waste tire pyrolysis are stored in tanks, moisture may accumulate in layers due to the water content of the raw materials or environmental condensation. This requires periodic drainage through a "water removal" operation to prevent oil emulsification, tank corrosion, or impact on downstream processing. Water removal is a drainage operation performed in oil tank farms in the petroleum and petrochemical industries, primarily to remove sediment from the bottom of the tanks.

[0003] The existing technologies for preparing emulsified asphalt have the following drawbacks: ① High cost and waste of resources in hazardous waste water treatment: Water from waste tire pyrolysis oil storage tanks is treated as hazardous waste, resulting in high costs and wasting potential organic resources; ② High cost and poor compatibility of added anti-aging agents: Traditional emulsified asphalt requires the additional purchase and addition of UV aging agents and antioxidants, which not only increases costs but also has limited compatibility with asphalt, making it prone to migration and precipitation; ③ Nano zinc oxide is prone to agglomeration and uneven dispersion: Existing zinc oxide-vermiculite composite materials are mostly physically mixed, and nano ZnO is extremely prone to agglomeration, failing to exert its due UV absorption and free radical capture efficiency; ④ Traditional anti-aging systems have single function and no long-term effect: Existing anti-aging agents are mostly disposable, with good initial effects but rapid failure in the later stages, lacking continuous protection capabilities; ⑤ Fenton oxidation causes excessive mineralization and damages organic resources: Conventional Fenton processes completely oxidize organic matter into CO2 and H2O, completely wasting the aromatic / heterocyclic structures that can be modified and utilized. Summary of the Invention

[0004] To address the above problems, this invention provides a method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks, comprising the following steps: S1, Water Cutting Pretreatment S1-1. The cut water is sent into the oil-water separation and equalization tank and left for 2-4 hours to separate and remove the upper floating oil and the bottom heavy tar. The middle effluent is discharged and filtered to retain suspended particles larger than 10μm to obtain the first-stage treated cut water. S1-2. Adjust the pH of the primary treated cut water to 6.0-8.0, then add polyaluminum chloride at a dosage of 100-500 mg / L and polyacrylamide at a dosage of 1-5 mg / L. After solid-liquid separation in a dissolved air flotation machine, scrape off the surface scum to obtain the secondary treated cut water. S1-3. The secondary treated water is introduced into the Fenton oxidation reactor, and H2O2 / Fe 2+Under the conditions of molar ratio 2-4:1 and pH 4.5-5.5, react for 20-30 min, adjust the pH of the reaction solution to 8.0-9.0, add NaHSO3, continuously monitor its redox potential until the redox potential of the reaction system drops below 150 mV, stop adding, and then stir for 10-20 min to obtain the three-stage treated water cut-off. Add 30% hydrogen peroxide via a metering pump, controlling the total addition time of H2O2 based on the entire reaction system volume, ensuring a uniform addition over 30-60 minutes. Add ferrous sulfate (FeSO4·7H2O) based on iron ions to reduce the Fe content in the reaction system. 2+ The initial concentration is 20-50 mg / L; the water temperature is maintained at 20-30℃ to avoid high temperature accelerating the free radical quenching side reaction; sodium hydroxide or lime milk is added to adjust the pH of the reaction solution to 8.0-9.0; Selective oxidation of water-soluble aromatic and heterocyclic compounds introduces phenolic hydroxyl and carboxyl groups, generating endogenous free radical scavengers, such as conventional Fenton (high H2O2 / Fe). 2+ Compared to low pH, which produces a large number of highly reactive hydroxyl radicals (·OH), which indiscriminately oxidize organic matter into CO2 and H2O (mineralization), mild Fenton, by precisely limiting the amount of free radicals produced and the reaction environment, only performs "partial oxidation" on molecules.

[0005] S1-4. The tertiary treated cut water is passed through a macroporous adsorption resin column, and then the effluent is passed through an ion exchange resin column until the conductivity of the effluent is less than 50 μS / cm. Finally, the pH is adjusted to 6.5-7.5 in a neutralization tank to obtain purified cut water. S2, Preparation of emulsified asphalt S2-1, Soap Liquid Preparation The refined water is heated to 45-55℃, and a cationic emulsifier is added at a mass percentage of 0.8-1.5%. The mixture is stirred evenly to form a soap solution, and industrial hydrochloric acid is added to adjust the pH of the soap solution to 6.5-7.5. S2-2, Asphalt Preparation The base asphalt is heated to 135-145℃ to obtain hot asphalt; S2-3, Colloid mill emulsification In a colloid mill, the hot asphalt and soap solution are sheared and emulsified at a mass ratio of 60-70:30-40. During the shearing and emulsification process, the colloid mill speed is 3000-5000 rpm, the emulsification time is 1-3 minutes of cyclic shearing, and the discharge temperature is 85-95℃ to obtain emulsified asphalt.

[0006] Furthermore, in order to adapt to the compositional fluctuations of water cut from different sources and to ensure the stability and effectiveness of the process, it is preferable to first perform compositional analysis on the mixed water cut. The method for compositional analysis is as follows: The water removal process was analyzed using GC-MS, FTIR, and ICP-OES to establish a database containing organic matter, heavy metal ions, and conventional physical properties. Based on the database information, the amount of Fenton's reagent in S1-3 can be fine-tuned to ensure the effect of directional oxidation. Subsequent practice has shown that as long as the main water removal indicators fall within the scope of this application, this scheme can be used directly to achieve stable production. Note: GC-MS can separate and identify specific organic compounds in a mixture, determining the concentrations of phenols, polycyclic aromatic hydrocarbons, heteroatom compounds, etc.; FTIR can determine the overall chemical bonds and functional groups present in the mixture; ICP-OES can accurately measure the concentration of metal ions, such as zinc ions, as well as calcium and sodium ions. Common physical properties include pH, COD, and surface tension. Through analysis, it can be clearly identified that there are both "harmful substances" that need to be removed from the water (such as heavy metal ions that catalytically age) and "beneficial substances" that can be utilized (aromatic / heterocyclic compounds that can be modified into antioxidants). This provides sufficient scientific basis for subsequent removal of metal ions by ion exchange and enrichment and reprocessing of endogenous protective agents by macroporous resins, realizing a closed loop of analysis and identification → selective removal / retention → directional modification → functionalized reuse.

[0007] Furthermore, in S1, the cut water is obtained by draining the bottom cut water from the waste tire pyrolysis oil storage tanks of 3-5 different pyrolysis plants and mixing them evenly; Explanation: The wastewater with the highest pollutant concentration is separated by physical sedimentation, and then a homogenized sample with complex composition and representativeness is obtained by mixing samples from different sources.

[0008] Further, in S1-4, the organic matter captured on the surface of the macroporous adsorption resin column is eluted with an organic solvent, the eluent is collected, and the eluent is returned to the purified water to make the total organic carbon concentration reach 50-200 mg / L. The elution method is as follows: First, soak the macroporous adsorption resin column with 1-2 times the resin bed volume of anhydrous ethanol or 0.1-0.5 mol / L sodium hydroxide solution for 15-30 min. Then, dynamically elute at a flow rate of 1-2 BV / h. Then, concentrate the eluent to 1 / 10-1 / 5 of the original volume by vacuum distillation under the conditions of jacket temperature of 40-50℃, absolute pressure of 20-40 mbar, and material residence time on the heating surface of <1 min, to obtain an eluent rich in aromatic and oxygen-containing heterocyclic compounds.

[0009] Instructions: The tertiary treated wastewater is passed through a macroporous adsorption resin (such as the Amberlite XAD series) specifically designed for adsorbing small-molecule aromatic and heterocyclic compounds. These endogenous UV absorbers and free radical scavengers are "enriched" and temporarily stored. After the column effluent has undergone ion exchange, the resin is eluted with a small amount of ethanol or alkaline solution, and the enriched protective organic matter is returned to the purified wastewater.

[0010] Furthermore, 1 / 5 to 1 / 3 of the tertiary treated water is collected for later use, and during the preparation of the S2-1 soap solution, 0.5-5 wt% of multifunctional micro-nano composite powder is added to the soap solution. The preparation method of the multifunctional micro-nano composite powder is as follows: (1) Preparation of UV absorber intercalated modified vermiculite By inserting benzotriazole or benzophenone UV absorbers into the interlayer of expanded vermiculite using a solution intercalation method, UV absorber-intercalated modified vermiculite is obtained. (2) Loading nano-ZnO hybrid particles onto vermiculite sheets The UV absorber intercalated modified vermiculite was ultrasonically dispersed in the three-stage treated water. Then, water-soluble zinc salt was added at a mass ratio of zinc salt to intercalated modified vermiculite of 1:2-5. The pH was adjusted to 8.0-9.0 at 40-60℃ and the reaction was carried out for 1-3 hours to obtain the reaction solution. (3) Post-processing The reaction solution was vacuum filtered for 2-8 minutes, and the filter cake was washed with deionized water until the washing solution was neutral. Then, it was rinsed 3-5 times with anhydrous ethanol at a wet weight of 0.5-1.0 mL / g of filter cake. Finally, it was vacuum dried at 60-80℃ and -0.08 to -0.095 MPa for 8-12 hours to obtain the multifunctional micro-nano composite powder.

[0011] Explanation: This method utilizes oxygen-containing functional groups from organic matter in water to complex zinc ions; the organic matter acts like "molecular wires," tightly encapsulating the surface of nano-zinc oxide. The absorbed ultraviolet light energy can be efficiently transferred to the zinc oxide core via non-radiative transitions, or the captured free radicals can be rapidly transferred to defect sites on the zinc oxide surface for annihilation. This significantly enhances the UV absorption efficiency and free radical capture capability of zinc oxide, achieving chemical-level synergy between endogenous and exogenous substances.

[0012] Vermiculite sheets act as a macroscopic physical barrier, blocking oxygen and ultraviolet radiation. Nano-sized ZnO hybrid particles are tightly anchored on the vermiculite surface, serving as microscopic chemical absorption points that efficiently absorb UV radiation and capture free radicals. This avoids the problem of easy aggregation when nanoparticles are added alone, ensuring their uniform dispersion and long-term stability in the asphalt. The organic UV absorbers between the vermiculite layers and the water-cutting organic matter bonded to the ZnO on the vermiculite surface together form a "UV capture net." The absorbed energy can be efficiently transferred and harmlessly dissipated along the pathway of "organic matter → ZnO" or "organic matter → organic matter between vermiculite layers," greatly broadening the effective absorption wavelength range.

[0013] Furthermore, in (1), inserting the ultraviolet absorber into the interlayer of expanded vermiculite by solution intercalation includes: Expanded vermiculite powder is dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and stirred at 60-80°C for 2-4 hours to obtain organo-modified vermiculite; wherein the amount of the aqueous solution of hexadecyltrimethylammonium bromide is 0.8-1.2 times the cation exchange capacity of vermiculite. Dissolve the UV absorber in a volatile organic solvent to prepare a 5-20 wt% UV absorber solution; The organically modified vermiculite is added to the ultraviolet absorber solution, with the amount of ultraviolet absorber being 5-15% of the vermiculite mass. The solution is then ultrasonically treated for 4-8 hours at 40-60°C, a frequency of 20-40 kHz, and a power of 150-400 W. The mixture is then stirred and evaporated at atmospheric pressure at 50-70°C and a rotation speed of 100-1000 r / min to obtain a filter cake. This filter cake is washed 2-4 times with ethanol at a wet weight of 0.5-1.0 mL / g. Finally, it is dried for 18-24 hours at an absolute pressure of 1-5 kPa and a temperature of 40-50°C until the moisture content of the filter cake is below 0.5 wt%, thus obtaining the ultraviolet absorber-intercalated modified vermiculite.

[0014] Note: After demulsification, the composite material is uniformly dispersed in the asphalt. Vermiculite layers provide physical oxygen barrier and UV shielding. When the asphalt develops acidic or polar groups due to aging, it slowly erodes the organic UV absorbers in the interlayers, causing them to release in a responsive manner. This forms a synergistic protection with the water-soluble endogenous absorbers in the asphalt through a "distribution gradient" and a "time gradient." Inorganic vermiculite shields the outer layer of UV, while water-absorbing organic matter is captured within the asphalt, and interlayer organic matter is released during the aging process, continuously replenishing the layer.

[0015] If intercalation is performed using ion exchange, the active sites between vermiculite layers will be saturated, resulting in the inability to effectively adsorb or anchor zinc ions, hindering the recombination reaction of in-situ generated ZnO hybrid particles, and severely depleting the retention of the reactivity between vermiculite layers; furthermore, due to the limited cation exchange capacity (CEC) of vermiculite and the large volume of cationic absorbents, the intercalation efficiency is usually very low.

[0016] Furthermore, the ultraviolet absorber is selected from benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers; the benzotriazole ultraviolet absorber is UV-326, and the benzophenone ultraviolet absorber is UV-531; the volatile organic solvent is ethanol, acetone, or ethyl acetate. Note: The benzotriazole structure of UV-326 is chemically very stable, heat-resistant, hydrolysis-resistant, and oxidation-resistant, and is not easily consumed. The benzophenone structure of UV-531 is also stable and can act as an auxiliary antioxidant to capture free radicals. It can form a synergistic mode of primary absorption and auxiliary scavenging with UV-326, protecting sensitive components in oils and also protecting UV-326 itself. Ethanol: Lowest toxicity, relatively safe and environmentally friendly, but may contain a small amount of water, making it unsuitable for water-sensitive systems. Acetone: Extremely strong dissolving power and fastest evaporation, making it an excellent cleaning and diluent, but extremely flammable. Ethyl acetate: Good dissolving power and has a fruity taste, with a much lower pungent odor than acetone, making it the preferred choice from an occupational health perspective, but also extremely flammable. Workers can flexibly choose the most suitable one among these three based on specific processes, safety regulations, and regulatory requirements.

[0017] Further, in (2), during the ultrasonic dispersion process, the ultrasonic frequency is 20-40 kHz, the ultrasonic power density is 50-100 W / L, and the ultrasonic time is 15-30 min; Note: The emulsified asphalt prepared with the above parameters has an ultra-fine particle size and uniform distribution; excellent storage stability; excellent workability; strong adhesion to aggregates; and excellent evaporation residue properties.

[0018] Furthermore, the mass-to-volume ratio of the organic UV absorber intercalated and modified vermiculite to the tertiary water treatment is 1g:20-50mL, preferably 1g:30mL; Note: At this ratio, the adsorption process typically exhibits an optimal combination of a rapid rise phase and a stable saturation phase. Compared to 20 mL, 30 mL increases the processing capacity by 50% and is more efficient. Compared to 50 mL, it has a stronger mass transfer driving force and can reach or approach the maximum saturation adsorption capacity in a shorter time, resulting in optimal working efficiency. If the solution volume is too small, the captured organic molecules will accumulate in large quantities on the surface of the vermiculite particles, potentially clogging the pores. This will hinder subsequent molecules from entering the interlayer for true "intercalation." A 1g:30mL ratio provides a sufficient aqueous environment, which helps the adsorbed molecules to rearrange orderly on the vermiculite surface and continuously diffuse into the depths of the interlayer, achieving stable and high-proportion intercalation.

[0019] Furthermore, vacuum filtration is performed using a microporous filter membrane with a pore size of 0.45-1 μm, under a relative vacuum of -0.04 to -0.06 MPa, and the cumulative thickness of the filter cake in a single filtration is controlled to not exceed 10 mm. Note: The selection of the pore size range directly addresses the size characteristics of vermiculite microparticles: ensuring complete product retention; preventing excessive fine powder clogging; and providing sufficient air / liquid permeability channels while guaranteeing near-absolute interception rates, significantly improving filtration efficiency. The vacuum level range prevents over-compaction of the filter cake. A sufficiently large pore size precisely intercepts the product, a just-right vacuum gently promotes separation, and strict control over the filter cake thickness ensures efficient, thorough, and repeatable filtration and washing.

[0020] Compared with existing technologies, the beneficial effects of this invention are: (1) This invention utilizes the water from the waste tire pyrolysis oil storage tank to replace clean water in the preparation of emulsified asphalt. It also uses mild Fenton technology to convert the soluble aromatic and heterocyclic compounds in the water into endogenous free radical scavengers and ultraviolet absorbers, achieving zero discharge of hazardous waste and “waste treatment”, which significantly reduces production costs and environmental disposal pressure.

[0021] (2) The present invention further uses pretreated water as a reaction medium and utilizes the oxygen-containing functional groups of organic matter therein to complex and anchor zinc ions, and grows nano zinc oxide-organic hybrid particles in situ on the intercalated modified vermiculite sheets, forming a chemically bonded micro-nano composite structure, which fundamentally solves the problem of easy agglomeration and uneven dispersion of nanoparticles in traditional physical mixing.

[0022] (3) This invention constructs a three-dimensional synergistic anti-aging system of "endogenous-exogenous-slow-release": vermiculite layers provide physical oxygen barrier and ultraviolet shielding, the ultraviolet absorber intercalated between the layers can be released responsively during the aging process, the in-situ grown nano-ZnO-organic hybrid particles serve as efficient ultraviolet absorption and free radical capture centers, and the endogenous organic matter cut into the water achieves bulk protection in the asphalt matrix. The three form a synergistic network of spatial gradient, temporal gradient and energy transfer, and the anti-aging performance is far superior to that of each component used alone or simple physical mixing, achieving a significant synergistic effect. Detailed Implementation

[0023] To further illustrate the methods and effects of this invention, the technical solution of this invention will be clearly and completely described below in conjunction with experiments.

[0024] Example 1: A method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks, comprising the following steps: S1, Water Cutting Pretreatment S1-1. The cut water is sent to an oil-water separation and equalization tank and left for 3 hours to separate and remove the upper layer of floating oil and the bottom heavy tar. The middle effluent is discharged and filtered to remove suspended particles larger than 10μm, resulting in primary treated cut water. In this embodiment, the filtration method is a dual-media filter of quartz sand and anthracite. This step can remove most of the non-dissolved pollutants and reduce the load on subsequent processes. S1-2. Adjust the pH of the primary treated cut water to 7.0, then add polyaluminum chloride at a dosage of 300 mg / L and polyacrylamide at a dosage of 3 mg / L. After solid-liquid separation in a dissolved air flotation (DAF) machine, scrape off the surface scum to obtain the secondary treated cut water. It is understood that the solid-liquid separation operation of the DAF machine is carried out using conventional methods in the art. For example, the dissolved air pressure is controlled at 0.4 MPa and the reflux ratio is 25%. S1-3. The secondary treated water is introduced into the Fenton oxidation reactor, and H2O2 / Fe 2+ The reaction was carried out at a molar ratio of 3:1 and a pH of 5 for 25 min. The pH of the reaction solution was then adjusted to 8.5, and NaHSO3 was added. The redox potential was continuously monitored until it dropped to 150 mV. The addition was then stopped, and the mixture was stirred for 15 min to obtain the three-stage treated water. S1-4. The tertiary treated cut water is passed through a macroporous adsorption resin column, and then the effluent from the column is passed through an ion exchange resin column. Finally, the pH is adjusted to 7.0 in a neutralization tank to obtain purified cut water. It is understandable that the conductivity of the effluent after passing through the column and then through the ion exchange resin column can be guaranteed to be below 50 μS / cm. In S1-4, the macroporous adsorption resin column was first soaked in 0.3 mol / L sodium hydroxide solution for 22 min, and then dynamically eluted at a flow rate of 1.5 BV / h. Then, it was concentrated to 3 / 20 of the original volume by vacuum distillation under the conditions of jacket temperature of 45℃, absolute pressure of 30 mbar, and material residence time on the heating surface of 40s, to obtain an eluent rich in aromatic and oxygen-containing heterocyclic compounds. The eluent was then added back to the purified water to make its total organic carbon concentration reach 130 mg / L. S2, Preparation of emulsified asphalt S2-1, Soap Liquid Preparation Heat the refined water to 50°C, add cationic emulsifier at a mass percentage of 1.2%, stir evenly to form soap solution, and add industrial hydrochloric acid to adjust the pH of the soap solution to 7.0; S2-2, Asphalt Preparation The base asphalt is heated to 140°C to obtain hot asphalt; S2-3, Colloid mill emulsification In a colloid mill, the hot asphalt and soap solution are sheared and emulsified at a mass ratio of 13:7. During the shearing and emulsification process, the colloid mill rotates at 4000 rpm, the emulsification time is 2 minutes of cyclic shearing, and the discharge temperature is 90℃ to obtain emulsified asphalt.

[0025] In S1, the cut water is obtained by draining the bottom cut water from the waste tire pyrolysis oil storage tanks of 5 different pyrolysis plants and mixing it evenly. Example 2: Unlike Example 1, in S1-1, the cut water is sent into the oil-water separation and conditioning tank and left for 2 hours; S1-2. Adjust the pH of the primary treated cut water to 6.0, then add polyaluminum chloride at a dosage of 100 mg / L and polyacrylamide at a dosage of 1 mg / L. After solid-liquid separation in a dissolved air flotation machine, scrape off the surface scum to obtain the secondary treated cut water.

[0026] Example 3: Unlike Example 1, in S1-1, the cut water is sent into the oil-water separation and conditioning tank and left for 4 hours; S1-2. Adjust the pH of the primary treated cut water to 8.0, then add polyaluminum chloride at a dosage of 500 mg / L and polyacrylamide at a dosage of 5 mg / L. After solid-liquid separation in a dissolved air flotation machine, scrape off the surface scum to obtain the secondary treated cut water.

[0027] Example 4: Unlike Example 1, in S1-3, the secondary treated water is introduced into the Fenton oxidation reactor, in H2O2 / Fe 2+ The reaction was carried out for 20 min at a molar ratio of 2:1 and a pH of 4.5.

[0028] Example 5: Unlike Example 1, in S1-3, the secondary treated water is introduced into the Fenton oxidation reactor, in H2O2 / Fe 2+ The reaction was carried out for 30 minutes at a molar ratio of 4:1 and a pH of 5.5.

[0029] Example 6: Unlike Example 1, in S1-3, the pH of the reaction solution was adjusted to 8.0, and NaHSO3 was added. The redox potential was continuously monitored until it dropped to 150 mV. The addition was then stopped, and the mixture was stirred for 10 min to obtain the three-stage treated water.

[0030] Example 7: Unlike Example 1, in S1-3, the pH of the reaction solution was adjusted to 9.0, and NaHSO3 was added. The redox potential was continuously monitored until it dropped to 120 mV. The addition was then stopped, and the mixture was stirred for 20 min to obtain the three-stage treated water.

[0031] Example 8: Unlike Example 1, in S1-4, the pH was adjusted to 6.5 in the neutralization tank to obtain refined cut water.

[0032] Example 9: Unlike Example 1, in S1-4, the pH is adjusted to 7.5 in the neutralization tank to obtain refined cut water.

[0033] Example 10: Unlike Example 1, in S1-4, the macroporous adsorption resin column was first soaked in anhydrous ethanol with 2 times the volume of the resin bed for 15 minutes.

[0034] Example 11: Unlike Example 1, in S1-4, the macroporous adsorption resin column was first soaked in 0.5 mol / L sodium hydroxide solution for 30 min.

[0035] Example 12: Unlike Example 1, in S1-4, dynamic elution was performed again at a flow rate of 1 BV / h, followed by vacuum distillation to concentrate the material to 1 / 5 of its original volume under the conditions of jacket temperature of 40°C, absolute pressure of 20 mbar, and material residence time on the heating surface of 30 s.

[0036] Example 13: Unlike Example 1, in S1-4, dynamic elution was performed again at a flow rate of 2 BV / h, followed by vacuum distillation to concentrate the material to 1 / 10 of its original volume under the conditions of jacket temperature of 50°C, absolute pressure of 40 mbar, and material residence time on the heating surface of 50 s.

[0037] Example 14: Unlike Example 1, in S1-4, the eluent is returned to the purified cutting water to make its total organic carbon concentration reach 50 mg / L.

[0038] Example 15: Unlike Example 1, in S1-4, the eluent was added back into the purified cutting water to make its total organic carbon concentration reach 200 mg / L.

[0039] Example 16: Unlike Example 1, S2-1, soap solution preparation Heat the refined water to 45°C, add cationic emulsifier at a mass percentage of 0.8%, stir until homogeneous to form soap solution, and add industrial hydrochloric acid to adjust the pH of the soap solution to 6.5.

[0040] Example 17: Unlike Example 1, S2-1, soap solution preparation Heat the refined water to 55°C, add cationic emulsifier at a mass percentage of 1.5%, stir until it becomes soap solution, and add industrial hydrochloric acid to adjust the pH of the soap solution to 7.5.

[0041] Example 18: Unlike Example 1, S2-2, asphalt preparation The base asphalt is heated to 135°C to obtain hot asphalt.

[0042] Example 19: Unlike Example 1, S2-2, asphalt preparation The base asphalt is heated to 45°C to obtain hot asphalt.

[0043] Example 20: Unlike Example 1, in S2-3, the hot asphalt and soap solution are sheared and emulsified in a colloid mill at a mass ratio of 6:4. During the shearing and emulsification process, the colloid mill speed is 3000 rpm, the emulsification time is 1 minute of cyclic shearing, and the discharge temperature is 85℃ to obtain emulsified asphalt.

[0044] Example 21: Unlike Example 1, in S2-3, the hot asphalt and soap solution are sheared and emulsified in a colloid mill at a mass ratio of 7:3. During the shearing and emulsification process, the colloid mill speed is 5000 rpm, the emulsification time is 3 minutes of cyclic shearing, and the discharge temperature is 95℃ to obtain emulsified asphalt.

[0045] Example 22: Unlike Example 1, 4 / 15 of the tertiary treatment water was collected for later use, and during the preparation of soap solution in S2-1, 2.5 wt% of multifunctional micro-nano composite powder was added to the soap solution. The preparation method of multifunctional micro-nano composite powder is as follows: (1) Preparation of organic ultraviolet absorber intercalated modified vermiculite UV-326 ultraviolet absorber was inserted into the interlayer of expanded vermiculite by solution intercalation to obtain UV absorber-intercalated modified vermiculite; The insertion of UV-326 ultraviolet absorber into the interlayer of expanded vermiculite via solution intercalation includes: Expanded vermiculite powder was dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and stirred at 70°C for 3 hours to obtain organo-modified vermiculite; wherein the amount of aqueous solution of hexadecyltrimethylammonium bromide was 1 times the cation exchange capacity of vermiculite; Dissolve the UV-326 ultraviolet absorber in ethanol to prepare a 12wt% solution; Organized vermiculite was added to this solution, with the amount of UV absorber being 10% of the vermiculite mass. The solution was ultrasonically treated at 50°C for 6 hours in a sealed container. The solution was then stirred and evaporated at 50-70°C under normal pressure to obtain a filter cake. The filter cake was washed three times with ethanol at a concentration of 0.8 mL / g based on its wet weight. The filter cake was then dried at an absolute pressure of 3 kPa and a temperature of 45°C for 21 hours until the moisture content of the filter cake was less than 0.5 wt%, thus obtaining UV absorber intercalated modified vermiculite. (2) Loading nano-ZnO hybrid particles onto vermiculite sheets UV absorber-intercalated modified vermiculite was ultrasonically dispersed in tertiary-treated water under the conditions of ultrasonic frequency: 30 kHz, ultrasonic power density: 75 W / L, and ultrasonic time: 22 min. Then, water-soluble zinc salt was added at a mass ratio of zinc salt to intercalated modified vermiculite of 1:4. The pH was adjusted to 8.5 at 50℃, and the reaction was carried out for 2 h to obtain the reaction solution. The mass-volume ratio of UV absorber-intercalated modified vermiculite to tertiary-treated water was 1 g: 30 mL. (3) Post-processing The reaction solution was vacuum filtered for 5 min, and the filter cake was washed with deionized water until the washing solution was neutral. Then, it was rinsed 4 times with anhydrous ethanol at a wet weight of 0.8 mL / g. Then, it was vacuum dried at 70℃ and -0.087 MPa for 10 h to obtain multifunctional micro-nano composite powder. The vacuum filtration was carried out using a microporous filter membrane with a pore size of 0.45-1 μm at a relative vacuum of -0.05 MPa, and the cumulative thickness of the filter cake in a single filtration was controlled to be 8 mm.

[0046] Example 23: Unlike Example 22, 1 / 5 of the tertiary treatment water was collected for later use, and during the preparation of soap solution in S2-1, 0.5 wt% of multifunctional micro-nano composite powder was added to the soap solution.

[0047] Example 24: Unlike Example 22, 1 / 3 of the tertiary treatment water was collected for later use, and during the preparation of soap solution in S2-1, 5 wt% of multifunctional micro-nano composite powder was added to the soap solution.

[0048] Example 25: (1) Preparation of organic ultraviolet absorber intercalated modified vermiculite The UV-326 ultraviolet absorber was inserted into the interlayer of expanded vermiculite by solution intercalation to obtain organic ultraviolet absorber intercalated vermiculite; The insertion of UV-326 ultraviolet absorber into the interlayer of expanded vermiculite via solution intercalation includes: Expanded vermiculite powder was dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and stirred at 60°C for 2 hours to obtain organo-modified vermiculite; wherein the amount of aqueous solution of hexadecyltrimethylammonium bromide was 0.8 times the cation exchange capacity of vermiculite. UV-326 ultraviolet absorber was dissolved in ethanol to prepare a 5 wt% ultraviolet absorber solution.

[0049] Example 26: (1) Preparation of organic ultraviolet absorber intercalated modified vermiculite The UV-326 ultraviolet absorber was inserted into the interlayer of expanded vermiculite by solution intercalation to obtain organic ultraviolet absorber intercalated vermiculite; The insertion of UV-326 ultraviolet absorber into the interlayer of expanded vermiculite via solution intercalation includes: Expanded vermiculite powder was dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and stirred at 80°C for 4 hours to obtain organo-modified vermiculite; wherein the amount of aqueous solution of hexadecyltrimethylammonium bromide was 1.2 times the cation exchange capacity of vermiculite. UV-326 ultraviolet absorber was dissolved in ethanol to prepare a 20wt% ultraviolet absorber solution.

[0050] Example 27: Unlike Example 22, in (1), the ultraviolet absorber is UV-531; the UV-531 ultraviolet absorber is dissolved in acetone.

[0051] Example 28: Unlike Example 22, in (1), UV-326 ultraviolet absorber was dissolved in ethyl acetate.

[0052] Example 29: Unlike Example 22, in (2), the UV absorber intercalated modified vermiculite was ultrasonically dispersed in the tertiary treatment water under the conditions of ultrasonic frequency: 20kHz, ultrasonic power density: 50 W / L, and ultrasonic time: 15-30min; the mass-volume ratio of UV absorber intercalated modified vermiculite to tertiary treatment water was 1g:20mL.

[0053] Example 30: Unlike Example 22, in (2), the UV absorber intercalated modified vermiculite was ultrasonically dispersed in the tertiary treatment water under the conditions of ultrasonic frequency: 40 kHz, ultrasonic power density: 100 W / L, and ultrasonic time: 30 min; the mass-volume ratio of UV absorber intercalated modified vermiculite to tertiary treatment water was 1 g: 50 mL.

[0054] Example 31: Unlike Example 22, in (2), water-soluble zinc salt was added at a mass ratio of 1:2 between zinc salt and intercalated modified vermiculite, and the pH was adjusted to 8.0 at 40°C for 1 hour.

[0055] Example 32: Unlike Example 22, in (2), water-soluble zinc salt was added at a mass ratio of 1:5 between zinc salt and intercalated modified vermiculite, and the pH was adjusted to 9.0 at 60°C for 3 hours.

[0056] Example 33: Unlike Example 22, in (3), the reaction solution was vacuum filtered for 2 min, the filter cake was washed with deionized water until the washing liquid was neutral, and then rinsed 3 times with anhydrous ethanol at a wet weight of 0.5 mL / g; during vacuum filtration, the filtration was carried out under a relative vacuum of -0.04 MPa.

[0057] Example 34: Unlike Example 22, in (3), the reaction solution was vacuum filtered for 8 minutes, the filter cake was washed with deionized water until the washing liquid was neutral, and then rinsed 5 times with anhydrous ethanol at a wet weight of 1.0 mL / g; during vacuum filtration, the filtration was carried out under a relative vacuum of -0.06 MPa.

[0058] Example 34: Unlike Example 22, in (3), the multifunctional micro-nano composite powder was obtained by vacuum drying at -80℃ and -0.08 MPa for 8 hours.

[0059] Example 35: Unlike Example 22, in (3), the multifunctional micro-nano composite powder was obtained by vacuum drying at 80℃ and -0.095 MPa for 12 hours.

[0060] Experimental Example: The description of this experimental example is based on the scheme described in Example 1, and aims to illustrate the practical application effect of the present invention.

[0061] 1. Experimental Design: Performance of UV-resistant emulsified asphalt: The performance of UV-resistant emulsified asphalt and the evaporation residue of the original emulsified asphalt were placed in an artificial high-intensity ultraviolet light source environment chamber (AIUREB) and subjected to strong ultraviolet radiation for 26 days (equivalent to 6 months of outdoor ultraviolet radiation intensity). The performance indicators are compared in Table 1. Control Group 1: Unlike Example 1, the refined water obtained in S1-4 was directly used for soap preparation without the eluent being recycled.

[0062] Control Group 2: Unlike Example 1, the pretreatment step of water cutting in S1 was removed, and the raw water cutting obtained by "mixing evenly from 5 pyrolysis plants" was used directly to prepare the soap solution.

[0063] Table 1. Comparison of anti-aging performance of Examples 1-21 and Control Groups 1-2

[0064] Conclusion: Table 1 shows that the performance differences of emulsified asphalt meeting the parameter ranges of Examples 1-21 of this application are small, and all indicators fluctuate within a reasonable range. This indicates that the present invention has a wide process window, high operational flexibility, and good industrial adaptability. Considering all factors, Example 1 is the optimal solution. In Comparative Example 1, the lack of eluent re-mixing led to a significant weakening of the anti-aging properties of the emulsified asphalt, and the performance of the prepared emulsified asphalt declined. This proves that the present invention, through a combination of mild Fenton extraction, macroporous adsorption resin enrichment, and vacuum distillation re-mixing, recovers water-soluble aromatic and heterocyclic compounds, allowing them to be added to the emulsified asphalt as endogenous soft components. This effectively compensates for the loss of light components during asphalt processing and use, thereby improving the flexibility and strength of the residue. The re-mixed organic matter effectively replenishes the soft components lost during asphalt aging, which is key to improving performance. In Comparative Example 2, the lack of pretreatment of the cut water prevented the formation of a stable emulsion, resulting in extremely poor evaporation performance. This demonstrates that high concentrations of pollutants (oils, suspended solids, salts, organic acids, etc.) in the original cut water severely damage the emulsifying ability of the emulsifier, leading to demulsification and stratification. Pretreatment is a fundamental prerequisite for process feasibility. Only through the pretreatment process of this invention can the cut water be transformed from "hazardous waste" into "resource".

[0065] 2. To investigate the effect of adding multifunctional micro-nano composite powder on the anti-aging properties of emulsified asphalt.

[0066] Comparative Example 3: Unlike Example 22, the powder added in S2-1 was changed to "a simple physical mixture of organic ultraviolet absorber, nano ZnO and expanded vermiculite, with the same total mass as the powder in Example 22".

[0067] Comparative Example 4: Unlike Example 22, the “three-stage water cutting” in step (2) is replaced with “refined water cutting (conductivity <50 μS / cm)”, and the rest is the same as in Example 22.

[0068] Conclusion: As can be seen from the data in Table 2, the properties of the emulsified asphalt obtained in Comparative Example 3 are inferior to those in Example 22. This proves that simple physical mixing cannot achieve uniform dispersion at the nanoscale, and the ultraviolet absorber and nano-ZnO cannot form a synergistic effect. In contrast, this invention, through in-situ growth, anchors nano-ZnO to the surface of vermiculite sheets via chemical bonding, achieving molecular-level dispersion and interfacial bonding. This intercalation-loading structure essentially enhances the powder's performance. Comparative Example 4 used nearly pure purified water, eliminating residual carboxyl, hydroxyl, and phenolic hydroxyl groups in the tertiary-treated water. These functional groups played a crucial "complexation anchoring" role in the synthesis process: they first captured Zn in the solution through coordination bonds. 2+This process enriches the ZnO crystals on the surface of the vermiculite flakes. Upon addition of alkali, the ZnO crystal nuclei preferentially nucleate and grow in situ at these anchoring points, rather than spontaneously precipitating in the solution. Without the anchoring mechanism, the uniformity of ZnO loading and its bonding strength decrease, leading to a reduction in the reinforcing efficiency of the final powder. This conversely proves that the residual organic matter in the water removed during tertiary treatment is not an impurity, but rather a functional aid for synthesizing highly efficient composite structures.

[0069] In summary, Example 22 is the optimal solution, which significantly improves high-temperature performance and long-term resistance to UV aging while ensuring good workability and low-temperature ductility.

Claims

1. A method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks, characterized in that, Includes the following steps: S1, Water Cutting Pretreatment S1-1. The cut water is sent into the oil-water separation and equalization tank and left for 2-4 hours to separate and remove the upper floating oil and the bottom heavy tar. The middle effluent is discharged and filtered to retain suspended particles larger than 10μm to obtain the first-stage treated cut water. S1-2. Adjust the pH of the primary treated cut water to 6.0-8.0, then add polyaluminum chloride at a dosage of 100-500 mg / L and polyacrylamide at a dosage of 1-5 mg / L. After solid-liquid separation in a dissolved air flotation machine, scrape off the surface scum to obtain the secondary treated cut water. S1-3. The secondary treated water is introduced into the Fenton oxidation reactor, and H2O2 / Fe 2+ Under the conditions of molar ratio 2-4:1 and pH 4.5-5.5, react for 20-30 min, adjust the pH of the reaction solution to 8.0-9.0, add NaHSO3, continuously monitor its redox potential until the redox potential of the reaction system drops below 150 mV, stop adding, and then stir for 10-20 min to obtain the three-stage treated water cut-off. S1-4. The tertiary treated cut water is passed through a macroporous adsorption resin column, and then the effluent is passed through an ion exchange resin column. Finally, the pH is adjusted to 6.5-7.5 in a neutralization tank to obtain purified cut water. S2, Preparation of emulsified asphalt S2-1, Soap Liquid Preparation The refined water is heated to 45-55℃, and a cationic emulsifier is added at a mass percentage of 0.8-1.5%. The mixture is stirred evenly to form a soap solution, and industrial hydrochloric acid is added to adjust the pH of the soap solution to 6.5-7.

5. S2-2, Asphalt Preparation The base asphalt is heated to 135-145℃ to obtain hot asphalt; S2-3, Colloid mill emulsification In a colloid mill, the hot asphalt and soap solution are sheared and emulsified at a mass ratio of 60-70:30-40. During the shearing and emulsification process, the colloid mill speed is 3000-5000 rpm, the emulsification time is 1-3 minutes of cyclic shearing, and the discharge temperature is 85-95℃ to obtain emulsified asphalt.

2. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 1, characterized in that, In S1-4, organic matter captured on the surface of the macroporous adsorption resin column is eluted with an organic solvent, the eluent is collected, and the eluent is returned to the purified water to make the total organic carbon concentration reach 50-200 mg / L. The elution method is as follows: First, soak the macroporous adsorption resin column with 1-2 times the resin bed volume of anhydrous ethanol or 0.1-0.5 mol / L sodium hydroxide solution for 15-30 min. Then, dynamically elute at a flow rate of 1-2 BV / h. Then, concentrate the eluent to 1 / 10-1 / 5 of the original volume by vacuum distillation under the conditions of jacket temperature of 40-50℃, absolute pressure of 20-40 mbar, and material residence time on the heating surface of <1 min.

3. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 1, characterized in that, Collect 1 / 5 to 1 / 3 of the tertiary treated water for later use, and add 0.5-5 wt% of multifunctional micro-nano composite powder to the soap solution during the preparation of S2-1 soap solution; The preparation method of the multifunctional micro-nano composite powder is as follows: (1) Preparation of UV absorber intercalated modified vermiculite UV absorber-intercalated vermiculite was obtained by intercalating a UV absorber between the layers of expanded vermiculite using a solution intercalation method. (2) Loading nano-ZnO hybrid particles onto vermiculite sheets The UV absorber intercalated modified vermiculite was ultrasonically dispersed in the three-stage treated water. Then, water-soluble zinc salt was added at a mass ratio of zinc salt to intercalated modified vermiculite of 1:2-5. The pH was adjusted to 8.0-9.0 at 40-60℃ and the reaction was carried out for 1-3 hours to obtain the reaction solution. (3) Post-processing The reaction solution was vacuum filtered for 2-8 minutes, and the filter cake was washed with deionized water until the washing solution was neutral. Then, it was rinsed 3-5 times with anhydrous ethanol at a wet weight of 0.5-1.0 mL / g of filter cake. Finally, it was vacuum dried at 60-80℃ and -0.08 to -0.095 MPa for 8-12 hours to obtain the multifunctional micro-nano composite powder.

4. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 3, characterized in that, In (1), the insertion of the ultraviolet absorber into the interlayer of expanded vermiculite by solution intercalation includes: Expanded vermiculite powder is dispersed in an aqueous solution of hexadecyltrimethylammonium bromide and stirred at 60-80°C for 2-4 hours to obtain organo-modified vermiculite; wherein the amount of the aqueous solution of hexadecyltrimethylammonium bromide is 0.8-1.2 times the cation exchange capacity of vermiculite. Dissolve the UV absorber in a volatile organic solvent to prepare a 5-20 wt% UV absorber solution; The organically modified vermiculite is added to the ultraviolet absorber solution, with the amount of ultraviolet absorber being 5-15% of the vermiculite mass. The solution is then ultrasonically treated for 4-8 hours at 40-60°C, a frequency of 20-40 kHz, and a power of 150-400 W. The mixture is then stirred and evaporated at atmospheric pressure at 50-70°C and a rotation speed of 100-1000 r / min to obtain a filter cake. This filter cake is washed 2-4 times with ethanol at a wet weight of 0.5-1.0 mL / g. Finally, it is dried for 18-24 hours at an absolute pressure of 1-5 kPa and a temperature of 40-50°C until the moisture content of the filter cake is below 0.5 wt%, thus obtaining the ultraviolet absorber-intercalated modified vermiculite.

5. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 4, characterized in that, The ultraviolet absorber is selected from benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers; the benzotriazole ultraviolet absorber is UV-326, and the benzophenone ultraviolet absorber is UV-531; the volatile organic solvent is ethanol, acetone, or ethyl acetate.

6. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 3, characterized in that, (2) In the ultrasonic dispersion process, the ultrasonic frequency is 20-40 kHz, the ultrasonic power density is 50-100 W / L, and the ultrasonic time is 15-30 min.

7. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 3, characterized in that, In (2), the mass-volume ratio of the organic ultraviolet absorber intercalated modified vermiculite to the three-stage treated water is 1g:20-50mL, preferably 1g:30mL.

8. The method for preparing emulsified asphalt based on water removal from waste tire pyrolysis oil storage tanks as described in claim 1, characterized in that, (3) Vacuum filtration is performed using a microporous filter membrane with a pore size of 0.45-1 μm, under a relative vacuum of -0.04 to -0.06 MPa, and the cumulative thickness of the filter cake in a single filtration is controlled to not exceed 10 mm.

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