Integrated preparation process of multifunctional oil-purifying cleaning agent

Abstract

The invention discloses an integrated preparation process of a multifunctional oil purifier, and relates to the technical field of oil purifier preparation, the preparation process comprises the following steps: a low-temperature primary mixing stage: pretreating a bio-based raw material, and preparing a primary nanoscale dispersion by a low-temperature dispersion technology; according to the invention, the problem of agglomeration of nanoparticles is solved through a nano-surfactant pre-assembly process in a low-temperature primary mixing stage by using a small-size effect and mild stirring, and the nanoparticles are endowed with an adsorption-catalysis-dispersion composite function through in-situ coating and synergistic assembly in a medium-temperature reaction stage, so that the oil stain decomposition and removal capability is enhanced, and the oil stain removal efficiency is improved. And in the final blending stage, through gradient particle size regulation and control, nanoparticles with different particle sizes act on a macroscopic oil film and a microscopic gap respectively, so that full-scale decontamination and precise matching of process parameters in each stage are realized, synergistic enhancement of dispersibility and functionality of the nanoparticles and product stability is ensured, storage layering is avoided, and the cleaning efficiency is remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of oil-purifying cleaning agent preparation technology, specifically an integrated preparation process for a multifunctional oil-purifying cleaning agent. Background Technology

[0002] Oil Cleaner is a high-efficiency cleaning product specifically designed for oily stains. It achieves rapid removal of stubborn oil stains through the chemical (emulsification, saponification, catalytic decomposition) and physical (penetration, adsorption, peeling) interactions between active ingredients and oil molecules. This type of product is indispensable in scenarios such as home kitchens, catering industry, food processing plants, and machinery repair workshops. It not only reduces the labor intensity of manual cleaning but also reduces hygiene hazards and equipment wear caused by oil accumulation. It has important practical value in improving cleaning efficiency and ensuring the safety of the production environment.

[0003] As cleaning demands continue to rise, traditional oil-removing cleaners are gradually revealing their performance shortcomings. The introduction of nanotechnology provides a new approach to solving these problems. Nanoparticles, with their extremely high specific surface area and surface activity, can significantly enhance their contact efficiency with oil molecules, theoretically leading to a substantial improvement in cleaning effectiveness.

[0004] However, existing technologies still face certain technical bottlenecks when applying nanoparticles to the preparation of oil-purifying cleaners. These technologies tend to cause nanoparticles to agglomerate, leading to the failure of active sites; they also have limited functionality, failing to simultaneously address oil stains of different sizes; they exhibit poor compatibility with mixing process parameters, resulting in product stratification and insufficient storage stability; and the dispersibility and functionality of nanoparticles are difficult to improve synergistically, hindering further optimization of cleaning efficiency. Therefore, developing an integrated preparation process for a multifunctional oil-purifying cleaner is of great significance. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an integrated preparation process for a multifunctional oil cleaner. This process addresses the problem of nanoparticle agglomeration and improves dispersion uniformity through a pre-assembly process in the low-temperature initial mixing stage; it endows nanoparticles with "adsorption-catalysis-dispersion" composite functions through in-situ coating and synergistic assembly in the medium-temperature reaction stage; it achieves precise removal of oil stains of different sizes through gradient particle size control in the final blending stage; and it achieves a synergistic enhancement effect on the dispersibility, functionality, and product stability of nanoparticles through precise matching of process parameters at each stage, thus comprehensively overcoming the limitations of existing technologies.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an integrated preparation process for a multifunctional oil-purifying cleaner, the preparation process comprising the following steps: In the low-temperature initial mixing stage, the bio-based raw materials are pretreated and a primary nanoscale dispersion is prepared by low-temperature dispersion technology. Under low-speed stirring of 50-150 r / min and 0-10℃ conditions, the primary nanoparticles are embedded in the gaps between surfactant molecules to form a "nano-surfactant" pre-assembly. In the intermediate temperature reaction stage, the system temperature is raised to 30-60℃ and the stirring speed is increased to 300-800r / min. Functional nanomaterials are introduced and a functional coating is formed on the surface of primary nanoparticles through in-situ coating reaction. Shear force is used to promote its synergistic assembly with detergent to form composite nano-aggregates. In the final blending stage, the remaining solvent is atomized and added. The nanoparticles are distributed in a gradient by particle size control technology, with small particles ranging from 10 to 50 nm and large particles ranging from 100 to 200 nm. The solvent addition rate and stirring parameters are controlled to achieve the gradient distribution of nanoparticles of different sizes.

[0007] Furthermore, the pretreatment in the low-temperature initial mixing stage includes screening and purifying the bio-based raw materials. After screening out bio-based raw materials with a purity of ≥95%, supercritical CO2 extraction is used to remove lipid-soluble impurities from the raw materials, followed by low-temperature dispersion treatment. The low-temperature dispersion technology is ultrasonic-assisted low-temperature grinding. In an environment of -5℃, the bio-based raw materials are continuously treated with 20kHz ultrasonic vibration for 20-30 minutes, while grinding is performed at a speed of 500r / min using a grinding device. The resulting primary nanoscale dispersion has a particle size of 50-100nm and a particle size variation coefficient of 5%-8%.

[0008] Furthermore, in the formation process of the "nano-surfactant" pre-assembly, the surfactant is first preheated at 0-10℃ for 10-15 min, and then a primary nano-scale dispersion is added. The mass ratio of the two is 1:4. The surfactant is sodium dodecylbenzenesulfonate. The reaction is carried out at a stirring speed of 50-150 r / min and at 0-10℃ for 45 min. The absolute value of the zeta potential of the pre-assembly is 30-40 mV, and the average particle size of the pre-assembly is 150-200 nm.

[0009] Furthermore, in the intermediate temperature reaction stage, nitrogen gas is introduced for protection before the system is heated, with a nitrogen flow rate of 0.5-1 L / min. Then, the temperature is gradually increased from 0-10℃ to 30-60℃ at a rate of 2℃ / min, while the stirring speed is simultaneously increased from 50-150 r / min to 300-800 r / min. The introduced functional nanomaterial is nano-TiO2, which is dried at 120℃ for 2 h before being added, with an average particle size of 20-30 nm, and the amount added is 1% of the total mass of the system.

[0010] Furthermore, in the in-situ coating reaction, the pH value of the system is first adjusted to 5.5-6.5, and then functional nanomaterials are added. The functional nanomaterials are bonded and coordinated by the hydroxyl groups on the surface of the primary nanoparticles. The reaction lasts for 30 minutes, during which the particle size change of the system is detected every 5 minutes. The resulting functional coating has a thickness of 7-8 nm and a porosity of 20%-30%.

[0011] Furthermore, in the formation of the composite nano-aggregates, the detergent additive is sodium tripolyphosphate, which is first prepared into an aqueous solution with a mass fraction of 20%, and then added dropwise to the system at a rate of 5 mL / min, with the amount added being 5% of the total mass of the system; the shear force generated by high-speed stirring is 70-80 Pa, and the particle size of the aggregates is monitored in real time by a laser particle size analyzer during the stirring process. The final composite nano-aggregates have a particle size of 300-400 nm and a specific surface area of ​​50-80 m² / g.

[0012] Furthermore, in the final blending stage, the remaining solvent is deionized water with a conductivity ≤10μS / cm. After being filtered through a 0.22μm filter membrane, it is added through an atomizing nozzle with a pore size of 0.3mm. The distance between the nozzle and the liquid surface is maintained at 30-40cm, the addition rate is 1mL / min, and the amount of deionized water added is 40%-50% of the total mass of the system. During the addition process, the system temperature is maintained at 30-35℃.

[0013] Furthermore, in the final blending stage, the particle size control technology includes using a dynamic light scattering instrument to monitor the particle size distribution in real time, controlling the distribution of nanoparticles by adjusting the stirring speed to 300 r / min, wherein small particles with a diameter of 10-50 nm account for 35%, and large particles with a diameter of 100-200 nm account for 65%; after the control is completed, 0.1%-0.2% of a stabilizer (sodium carboxymethyl cellulose) is added to the system, and the pH value of the system is controlled to 8.0, and the surface tension is controlled to 35 mN / m.

[0014] Compared with existing technologies, the integrated manufacturing process of this multifunctional oil-purifying cleaner has the following advantages: This invention utilizes a "nano-surfactant" pre-assembly process in the low-temperature initial mixing stage to solve the problem of nanoparticle agglomeration and improve dispersion uniformity by leveraging the small size effect and gentle stirring. In the medium-temperature reaction stage, in-situ coating and synergistic assembly endow the nanoparticles with "adsorption-catalysis-dispersion" composite functions, enhancing their ability to decompose and remove oil stains. In the final blending stage, gradient particle size control allows nanoparticles of different sizes to act on both the macroscopic oil film and microscopic gaps, achieving full-scale decontamination. The precise matching of process parameters at each stage ensures a synergistic enhancement of nanoparticle dispersibility, functionality, and product stability, avoiding storage stratification and significantly improving cleaning efficiency.

[0015] Other advantages, objectives and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination or study, or may be learned from the practice of the invention. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0017] Figure 1 This is a flowchart of the integrated preparation process for a multifunctional oil-purifying cleaner. Detailed Implementation

[0018] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided below.

[0019] The integrated preparation process of the multifunctional oil-cleaning cleaner disclosed in this invention achieves efficient dispersion, functional compounding, and gradient distribution of nanoparticles through precise staged control of process parameters, significantly improving the product's cleaning performance and stability. (See also...) Figure 1 The specific implementation process is as follows: First, the bio-based raw materials are screened and purified. Raw materials with a purity of ≥95% are selected and supercritical CO2 extraction technology is used to remove fat-soluble impurities to ensure the cleanliness of the raw materials. Then, the materials are dispersed by ultrasonic-assisted low-temperature grinding: the raw materials are continuously treated with 20kHz ultrasonic vibration for 20-30 minutes in an environment of -5℃, while grinding is carried out at a speed of 500r / min. Finally, a primary nanoscale dispersion with a particle size of 50-100nm and a particle size variation coefficient of 5%-8% is produced.

[0020] The surfactant is preheated at 0-10℃ for 10-15 min, and then added to the primary nanoscale dispersion at a mass ratio of 1:4. The mixture is stirred at a low speed of 50-150 r / min and reacted at 0-10℃ for 45 min, so that the primary nanoparticles are embedded in the intermolecule gaps of the surfactant to form a pre-assembled body with an absolute Zeta potential of 30-40 mV and an average particle size of 150-200 nm, which effectively solves the problem of nanoparticle aggregation.

[0021] Nitrogen gas was introduced into the pre-assembled system for protection, and the temperature was raised to 30-60℃ at a rate of 2℃ / min. At the same time, the stirring speed was increased to 300-800r / min. Nano TiO2 that had been dried at 120℃ for 2h was introduced, with the amount added being 1% of the total mass of the system.

[0022] First, the pH of the system is adjusted to 5.5-6.5, so that the hydroxyl groups on the surface of the primary nanoparticles and nano TiO2 undergo an in-situ coating reaction through bonding and coordination. Within 30 minutes, a functional coating with a thickness of 7-8 nm and a porosity of 20%-30% is formed. Then, the detergent is added to the system at a rate of 5 mL / min. The shear force of 70-80 Pa is used to promote its co-assembly with the coated nanoparticles, and finally a composite nano-aggregate with a particle size of 300-400 nm and a specific surface area of ​​50-80 m² / g is formed, which endows it with the composite function of "adsorption-catalysis-dispersion".

[0023] Deionized water with a conductivity ≤10μS / cm was selected as the residual solvent. After being filtered through a 0.22μm filter membrane, it was added to the system through an atomizing nozzle with a pore size of 0.3mm. The addition rate was controlled at 1mL / min, and the system temperature was maintained at 30-35℃ during the addition process. The amount added was 40%-50% of the total mass of the system.

[0024] The particle size distribution was monitored in real time using a dynamic light scattering instrument. By adjusting the stirring speed to 300 r / min, the nanoparticles were made to exhibit a gradient distribution: 35% of the particles were small in diameter (10-50 nm) and 65% were large in diameter (100-200 nm). These particles acted on the micro-cracks and macro-oil film respectively, achieving full-scale decontamination. Finally, 0.1%-0.2% of a stabilizer was added to control the pH value of the system to 8.0 and adjust the surface tension to 35 mN / m to ensure that the product does not separate during storage and has excellent stability.

[0025] Through the above process, the parameters at each stage are precisely matched, synergistically enhancing the dispersibility, functionality, and product stability of nanoparticles, and significantly improving the efficiency of the oil cleaner in decomposing and removing oil stains.

[0026] Example 1 I. Low-temperature initial mixing stage Bio-based raw materials were pretreated and screened to obtain bio-based raw materials (such as plant oil derivatives) with a purity of 96%. Supercritical CO2 extraction technology was used to remove fat-soluble impurities. The extraction pressure was controlled at 30 MPa, the temperature at 40℃, and the extraction time at 2 hours.

[0027] Dispersion was performed using an ultrasonic-assisted low-temperature grinding method: In a low-temperature environment of -5℃, a 20kHz ultrasonic vibration device was started, and the grinding device speed was adjusted to 500r / min. The pretreated bio-based raw materials were continuously processed for 25min to produce a primary nanoscale dispersion. The particle size was measured to be 70nm and the particle size variation coefficient was 6%.

[0028] A "nano-surfactant" pre-assembly was formed, using sodium dodecylbenzenesulfonate as the surfactant, and preheated at 5°C for 12 min.

[0029] The primary nanoscale dispersion was added to the surfactant at a mass ratio of 1:4, and the mixture was reacted at a stirring speed of 80 r / min and a temperature of 5°C for 45 min to form a pre-assembled structure. The pre-assembled structure was found to have an absolute zeta potential of 35 mV and an average particle size of 180 nm.

[0030] II. Mesotemperature reaction stage For system preparation and heating, nitrogen gas is introduced into the pre-assembled system at a flow rate of 0.8 L / min for 3 minutes for protection.

[0031] The system temperature was increased from 5℃ to 45℃ at a rate of 2℃ / min, while the stirring speed was simultaneously increased from 80r / min to 500r / min.

[0032] Functional nanomaterials were introduced and reacted. Nano-TiO2 with an average particle size of 25 nm was selected as the functional nanomaterial. It was first dried at 120 °C for 2 h, and then added to the system at a ratio of 1% of the total mass of the system.

[0033] The pH of the system was adjusted to 6.0 with dilute hydrochloric acid. The hydroxyl groups on the surface of the primary nanoparticles were bonded and coordinated with the nano-TiO2. The reaction was continued for 30 minutes. During this period, the particle size of the system was detected every 5 minutes using a laser particle size analyzer. Finally, a functional coating with a thickness of 7.5 nm and a porosity of 25% was formed.

[0034] To form composite nano-aggregates, sodium tripolyphosphate was prepared into an aqueous solution with a mass fraction of 20% and added dropwise to the system at a rate of 5 mL / min, with the amount added being 5% of the total mass of the system.

[0035] Maintaining a stirring speed of 500 r / min (generating a shear force of 75 Pa) promotes the co-assembly of the aggregate with the detergent to form a composite nano-aggregate. The particle size was measured to be 350 nm and the specific surface area was 65 m² / g.

[0036] III. Final Harmonization Stage Add the remaining solvent. Deionized water with a conductivity of 8 μS / cm was selected as the remaining solvent. It was first filtered through a 0.22 μm filter membrane and then added to the system through an atomizing nozzle with an aperture of 0.3 mm. The distance between the nozzle and the liquid surface was kept at 35 cm. The addition rate was 1 mL / min, and the addition amount was 45% of the total mass of the system. The system temperature was maintained at 32℃ during the addition process.

[0037] Particle size control and stabilization were achieved by using a dynamic light scattering instrument to monitor the particle size distribution of the system in real time. The stirring speed was adjusted to 300 r / min to control the nanoparticles to exhibit a gradient distribution, with small particles of 10-50 nm accounting for 35% and large particles of 100-200 nm accounting for 65%.

[0038] Add 0.15% sodium carboxymethyl cellulose as a stabilizer to the system, adjust the pH of the system to 8.0 with sodium hydroxide, and test its surface tension to be 35 mN / m, thus completing the preparation of the multifunctional oil purifier.

[0039] This embodiment, through precise control of process parameters at each stage, produces an oil-removing cleaner with good dispersibility, stability, and detergency.

[0040] Example 2 I. Low-temperature initial mixing stage Bio-based raw material pretreatment: Bio-based raw materials with a purity of 95% (such as palm oil fatty acid methyl ester) are screened out, and supercritical CO2 extraction technology is used to remove fat-soluble impurities. During the extraction process, the pressure is controlled at 28MPa and the temperature at 38℃, and the extraction is continued for 1.5h to ensure that the residual amount of impurities is ≤0.5%.

[0041] Dispersion was carried out using ultrasonic-assisted low-temperature grinding: In a constant-temperature reactor at -5℃, a 20kHz ultrasonic vibration device was started, and the grinding device speed was adjusted to 500r / min. The extracted bio-based raw materials were continuously processed for 20min. After processing, the particle size of the primary nanoscale dispersion was measured by a laser particle size analyzer. The particle size variation coefficient was 50nm, and the dispersion uniformity was good.

[0042] To form a "nano-surfactant" pre-assembly, sodium dodecylbenzenesulfonate was weighed as the surfactant and placed in a constant temperature water bath at 0℃ for 10 minutes to preheat its molecular activity.

[0043] The primary nanoscale dispersion was slowly added to the surfactant at a mass ratio of 1:4. The reaction was carried out at a stirring speed of 50 r / min and at 0℃ for 45 min. After the reaction was completed, the zeta potential of the pre-assembled particles was detected by a dynamic light scattering instrument. The absolute value of the zeta potential was 30 mV and the average particle size was 150 nm, showing a stable dispersion state.

[0044] II. Mesotemperature reaction stage For system preparation and heating, nitrogen gas is introduced into the pre-assembled system at a flow rate of 0.5 L / min for 2 minutes to remove air from the system and avoid interference from the oxidation reaction.

[0045] Start the heating device and raise the system temperature from 0℃ to 30℃ at a rate of 2℃ / min, while simultaneously increasing the stirring speed from 50r / min to 300r / min to ensure that the system temperature and stirring intensity change in tandem.

[0046] Functional nanomaterials were introduced and reacted. Nano-TiO2 with an average particle size of 20 nm was selected as the functional nanomaterial. It was first dried in an oven at 120 °C for 2 h to remove moisture and surface adsorbed impurities. Then, it was precisely added to the system at a ratio of 1% of the total mass of the system.

[0047] The pH of the system was adjusted to 5.5 with dilute hydrochloric acid. At this time, the hydroxyl groups (-OH) on the surface of the primary nanoparticles bonded and coordinated with the nano TiO2. The reaction continued for 30 minutes. During this period, the particle size change was detected every 5 minutes using a laser particle size analyzer. The final functional coating had a thickness of 7 nm and a porosity of 20%. The coating was found to have a rich microporous structure by nitrogen adsorption method.

[0048] To form composite nano-aggregates, sodium tripolyphosphate was dissolved in deionized water to prepare a 20% aqueous solution. This solution was then added dropwise to the system at a rate of 5 mL / min using a constant flow pump, with the amount added being 5% of the total mass of the system.

[0049] Maintaining a stirring speed of 300 r / min, the system generates a shear force of 70 Pa, which promotes the co-assembly of primary nanoparticles and sodium tripolyphosphate. After the reaction, the particle size of the composite nanoaggregates is 300 nm and the specific surface area is 50 m² / g. The regular aggregate structure can be observed by scanning electron microscopy.

[0050] III. Final Harmonization Stage The remaining solvent was added. Deionized water with a conductivity of 10 μS / cm was selected as the remaining solvent. After filtering through a 0.22 μm filter membrane to remove particulate impurities, it was added to the system through an atomizing nozzle with an aperture of 0.3 mm. The distance between the nozzle and the liquid surface was maintained at 30 cm, and the addition rate was controlled at 1 mL / min. The amount added was 40% of the total mass of the system. During the addition process, the system temperature was maintained at 30℃ using a thermostat to avoid temperature fluctuations affecting particle distribution.

[0051] Particle size control and stabilization were achieved by using a dynamic light scattering instrument to monitor the particle size distribution of the system in real time and adjusting the stirring speed to 300 r / min. Ultimately, the proportion of small particles with a diameter of 10-50 nm was 35%, and the proportion of large particles with a diameter of 100-200 nm was 65%, thus achieving a gradient distribution.

[0052] Add 0.1% sodium carboxymethyl cellulose as a stabilizer to the system, and adjust the pH of the system to 8.0 with 0.1 mol / L sodium hydroxide solution. The surface tension of the system was measured to be 35 mN / m by a surface tension meter, which meets the requirements for use of cleaning products.

[0053] Example 3 I. Low-temperature initial mixing stage Bio-based raw material pretreatment: Select bio-based raw materials with a purity of 97% (such as coconut oil alcohol polyoxyethylene ether), and use supercritical CO2 extraction technology to remove fat-soluble impurities. The extraction pressure is 32MPa, the temperature is 42℃, and the extraction is carried out continuously for 2.5h to ensure that the purity of the raw materials is stable at above 97%.

[0054] Dispersion was achieved using ultrasonic-assisted low-temperature grinding: In a constant-temperature reactor at -5℃, a 20kHz ultrasonic vibration device was started, and the grinding device speed was adjusted to 500r / min. The raw material was continuously processed for 30min. After processing, the particle size of the primary nanoscale dispersion was 100nm, and the particle size variation coefficient was 8%. Transmission electron microscopy showed that the particles were uniformly dispersed without obvious agglomeration.

[0055] A "nano-surfactant" pre-assembly was formed by using sodium dodecylbenzenesulfonate as the surfactant and preheating it in a constant temperature water bath at 10°C for 15 minutes.

[0056] The surfactant and primary nanoscale dispersion were mixed at a mass ratio of 1:4 and reacted at a stirring speed of 150 r / min and 10 °C for 45 min. After the reaction was completed, the zeta potential of the pre-assembled body was 40 mV, the average particle size was 200 nm, and the colloidal stability was excellent.

[0057] II. Mesotemperature reaction stage For system preparation and heating, nitrogen gas is introduced into the pre-assembled system at a flow rate of 1 L / min for 4 min to completely remove air.

[0058] The system temperature was increased from 10℃ to 60℃ at a rate of 2℃ / min, while the stirring speed was increased from 150r / min to 800r / min to ensure that the system was in a uniform mixing state.

[0059] Functional nanomaterials were introduced and reacted. Nano-TiO2 with an average particle size of 30 nm was selected and dried at 120 °C for 2 h. It was then added at a ratio of 1% of the total mass of the system. The pH of the system was adjusted to 6.5 with dilute hydrochloric acid to fully bond the hydroxyl groups on the surface of the primary nanoparticles with the nano-TiO2. After reacting for 30 min, a functional coating with a thickness of 8 nm and a porosity of 30% was formed. The density of catalytic active sites in the coating was increased by 20% compared with that before treatment.

[0060] To form composite nano-aggregates, sodium tripolyphosphate was prepared into a 20% aqueous solution and added dropwise to the system at a rate of 5 mL / min, with the amount added being 5% of the total mass of the system. Under stirring speed of 800 r / min (shear force 80 Pa), composite nano-aggregates were formed. The particle size was measured to be 400 nm, the specific surface area was 80 m² / g, and the adsorption capacity was significantly enhanced.

[0061] III. Final Harmonization Stage Add the remaining solvent. Use deionized water with a conductivity of 5 μS / cm. After filtering through a 0.22 μm filter membrane, add it to the system through an atomizing nozzle with a pore size of 0.3 mm. The distance between the nozzle and the liquid surface is 40 cm. The addition rate is 1 mL / min. The amount added is 50% of the total mass of the system. During the addition process, the system temperature is maintained at 35℃ to ensure uniform solvent dispersion.

[0062] Particle size control and stabilization were performed using a dynamic light scattering instrument. The stirring speed was adjusted to 300 r / min to ensure that the proportion of small particles (10-50 nm) was 35% and the proportion of large particles (100-200 nm) was 65%. 0.2% sodium carboxymethyl cellulose was added as a stabilizer, and the pH of the system was adjusted to 8.0, with a surface tension of 35 mN / m. The product stability and performance met the standards.

[0063] Comparative Example Low-temperature treatment stage: 85% pure bio-based raw materials (unpurified) were selected and stirred at 200 r / min for 30 min in a conventional reactor at 20℃ to prepare a dispersion with a particle size of 200-300 nm (particle size variation coefficient 25%). No surfactant was added, and no "nano-surfactant" pre-assemblies were formed. The particle agglomeration phenomenon was obvious.

[0064] In the intermediate temperature reaction stage: the system temperature was directly raised to 40℃, the stirring speed was maintained at 200r / min, and undried nano-TiO2 (average particle size 40nm, moisture content 5%) was added at 1% of the total mass of the system. The pH value was not adjusted (natural pH=6.8), and no in-situ coating reaction was performed. Sodium tripolyphosphate (20% aqueous solution, 5% of the total mass of the system) was added directly. After stirring for 10min, no obvious composite nano-aggregates were formed in the system, and the particles were dispersed randomly.

[0065] Final blending stage: Deionized water with a conductivity of 20 μS / cm was directly poured into the system (without atomization or filtration), accounting for 45% of the total mass of the system. The stirring speed was 200 r / min. No particle size control was performed. The particle size distribution of the nanoparticles was 50-300 nm (without a clear proportion). No stabilizer was added. The pH value of the system was 7.0, and the surface tension was 45 mN / m. After one week of storage at room temperature, obvious stratification appeared.

[0066]

[0067] As can be seen from the table above, Examples 1, 2, and 3 all strictly followed the integrated preparation process of the present invention. Through key steps such as bio-based raw material purification, "nano-surfactant" pre-assembly, in-situ coating, and gradient particle size control, the dispersibility, functionality, and stability of the nanoparticles in the product were ensured. The differences among the three examples mainly lie in the purity of the raw materials and the details of the process parameters (such as temperature and stirring speed). All three examples can achieve efficient decontamination. The comparative example, due to the lack of core processes (such as unpurified raw materials, no pre-assembled components, no in-situ coating, and no particle size control), resulted in severe particle agglomeration, lack of functionality, poor stability, high surface tension, and decontamination ability and storage performance far lower than those of the examples. This fully demonstrates the key role of the process of the present invention in improving the performance of the oil-removing cleaner.

[0068] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. An integrated manufacturing process for a multifunctional oil-purifying cleaner, characterized in that, The preparation process includes the following steps: In the low-temperature initial mixing stage, the bio-based raw materials are pretreated and a primary nanoscale dispersion is prepared by low-temperature dispersion technology. Under low-speed stirring of 50-150 r / min and 0-10℃ conditions, the primary nanoparticles are embedded in the gaps between surfactant molecules to form a "nano-surfactant" pre-assembly. In the intermediate temperature reaction stage, the system temperature is raised to 30-60℃ and the stirring speed is increased to 300-800r / min. Functional nanomaterials are introduced and a functional coating is formed on the surface of primary nanoparticles through in-situ coating reaction. Shear force is used to promote its synergistic assembly with detergent to form composite nano-aggregates. In the final blending stage, the remaining solvent is atomized and added. The nanoparticles are distributed in a gradient by particle size control technology, with small particles ranging from 10 to 50 nm and large particles ranging from 100 to 200 nm. The solvent addition rate and stirring parameters are controlled to achieve the gradient distribution of nanoparticles of different sizes.

2. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, The pretreatment in the low-temperature initial mixing stage includes screening and purifying the bio-based raw materials. After screening out bio-based raw materials with a purity of ≥95%, supercritical CO2 extraction is used to remove lipid-soluble impurities from the raw materials, followed by low-temperature dispersion treatment. The low-temperature dispersion technology is ultrasonic-assisted low-temperature grinding. In an environment of -5℃, the bio-based raw materials are continuously treated with 20kHz ultrasonic vibration for 20-30 minutes, while grinding is performed at a speed of 500r / min using a grinding device. The resulting primary nanoscale dispersion has a particle size of 50-100nm and a particle size variation coefficient of 5%-8%.

3. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the formation of the "nano-surfactant" pre-assembly, the surfactant is first preheated at 0-10℃ for 10-15 min, and then a primary nano-scale dispersion is added. The mass ratio of the two is 1:

4. The surfactant is sodium dodecylbenzenesulfonate. The reaction is carried out at a stirring speed of 50-150 r / min and at 0-10℃ for 45 min. The absolute value of the zeta potential of the pre-assembly is 30-40 mV, and the average particle size of the pre-assembly is 150-200 nm.

4. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the intermediate temperature reaction stage, nitrogen gas is introduced for protection before the system is heated, with a nitrogen flow rate of 0.5-1 L / min. Then, the temperature is gradually increased from 0-10℃ to 30-60℃ at a rate of 2℃ / min, while the stirring speed is simultaneously increased from 50-150 r / min to 300-800 r / min. The introduced functional nanomaterial is nano-TiO2, which is dried at 120℃ for 2 h before being added, with an average particle size of 20-30 nm, and the amount added is 1% of the total mass of the system.

5. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the in-situ coating reaction, the pH value of the system is first adjusted to 5.5-6.5, and then functional nanomaterials are added. The functional nanomaterials are bonded and coordinated by the hydroxyl groups on the surface of the primary nanoparticles. The reaction lasts for 30 minutes, and the particle size change of the system is detected every 5 minutes. The resulting functional coating has a thickness of 7-8 nm and a porosity of 20%-30%.

6. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the formation of the composite nano-aggregates, the detergent additive is sodium tripolyphosphate, which is first prepared into an aqueous solution with a mass fraction of 20%, and then added dropwise to the system at a rate of 5 mL / min, with the amount added being 5% of the total mass of the system; the shear force generated by high-speed stirring is 70-80 Pa, and the particle size of the aggregates is monitored in real time by a laser particle size analyzer during the stirring process. The final composite nano-aggregates have a particle size of 300-400 nm and a specific surface area of ​​50-80 m² / g.

7. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the final blending stage, the remaining solvent is deionized water with a conductivity ≤10μS / cm. It is first filtered through a 0.22μm filter membrane and then added through an atomizing nozzle with a pore size of 0.3mm. The distance between the nozzle and the liquid surface is maintained at 30-40cm, the addition rate is 1mL / min, and the amount of deionized water added is 40%-50% of the total mass of the system. During the addition process, the system temperature is maintained at 30-35℃.

8. The integrated preparation process of a multifunctional oil-purifying cleaner according to claim 1, characterized in that, In the final blending stage, the particle size control technology includes using a dynamic light scattering instrument to monitor the particle size distribution in real time, and controlling the distribution of nanoparticles by adjusting the stirring speed to 300 r / min, wherein small particles with a diameter of 10-50 nm account for 35% and large particles with a diameter of 100-200 nm account for 65%; after the control is completed, 0.1%-0.2% of stabilizer is added to the system, and the pH value of the system is controlled to 8.0 and the surface tension is controlled to 35 mN / m.

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