Super-micro associated emulsion profile control agent and preparation method thereof

Abstract

This invention relates to an ultra-micro associative emulsion modifier, belonging to the technical field of chemical flooding agents used in oilfield chemistry to enhance oil recovery. It addresses the problems of insufficient interfacial activity, poor emulsion stability, and limited permeability in formation pores caused by improper surfactant formulation in existing modifiers. The key technical point is to provide a composite system composed of water, polyether-modified polysiloxane, sodium α-olefin sulfonate, and sodium dodecyl sulfate in specific weight proportions. Through molecular synergy and association among the components, this system spontaneously forms ultra-fine and stable emulsion droplets, effectively reducing the oil-water interfacial tension and enhancing the long-term stability of the system in complex formation environments. Its main application is as a modifier in oilfield water injection development, adjusting the water flow profile by injecting it into the formation, emulsifying and carrying residual oil, thereby improving oil displacement efficiency and increasing the ultimate oil recovery rate.

Description

Technical Field

[0001] This invention belongs to the technical field of chemical flooding agents used to enhance oil recovery in oilfield chemistry. More specifically, this invention relates to ultra-micro associative emulsion flooding agents and their preparation methods. Background Technology

[0002] In chemical flooding operations in oilfields, surfactant systems are commonly used as modifiers to reduce oil-water interfacial tension, improve water flow profiles, and thus enhance oil recovery. Current technologies generally employ single surfactants or simple mixtures of several surfactants to formulate these systems. However, these conventional systems have gradually revealed several shortcomings in practical applications.

[0003] First, single-type surfactants often have limitations in reducing oil-water interfacial tension. Due to their simple molecular structure, their arrangement and adsorption behavior at the oil-water interface are insufficient, making it difficult to continuously reduce the interfacial tension to the ideal level. Incomplete reduction of interfacial tension directly affects the emulsification and carrying capacity of the displacement fluid for residual oil, resulting in low micro-displacement efficiency. This phenomenon is caused by the limited adaptability of single surfactants to the complex reservoir environment; their interfacial activity is prone to fluctuation under conditions of formation water salinity, temperature changes, or different crude oil compositions.

[0004] Secondly, attempts to simply mix different surfactants physically often encounter technical difficulties. For example, when directly mixing ionic and nonionic surfactants, improper ratio control can easily lead to precipitation or phase separation due to charge interactions. This not only disrupts the homogeneity of the system but may also significantly reduce interfacial activity. Even among ionic surfactants, antagonistic effects may occur without proper molecular design and formulation support, resulting in interfacial performance that is actually lower than that of the single component. This uncertainty in formulation leads to extensive trial and error in the formulation development process, and the window for successful formulation is often narrow, posing challenges to quality control in large-scale production.

[0005] Furthermore, the micelles or emulsion droplets formed by conventional surfactant systems are typically not fine enough and have a wide distribution. Larger droplet sizes are easily physically hindered when passing through the fine pores of the reservoir, and may even become trapped at the pore throat, affecting the effective migration of the modulator to deeper reservoirs. This is mainly because simple mixing systems have weak ability to regulate the molecular aggregate structure and cannot actively guide the formation of uniformly sized, structurally stable ultrafine aggregates. Simultaneously, when the system is left to stand for a long time or experiences temperature fluctuations, it is prone to stratification, precipitation, or uneven distribution of active ingredients, leading to performance degradation over time and failing to meet the requirements for storage stability of modulators in oilfields.

[0006] To address the aforementioned issues, efforts have been made in this field to develop novel surfactant monomers or optimize compounding processes. However, the synthesis of novel structural surfactants is costly, and their universality under different reservoir conditions still requires long-term verification. When searching for effective compounding solutions among commonly used surfactants, achieving synergistic effects between different types of surfactant molecules, rather than simple additive or offsetting effects, has become a key challenge. Specifically, it is necessary to overcome multiple difficulties, such as poor compatibility of different molecules in solution, competitive adsorption at interfaces leading to disordered arrangement, and the easy disintegration of associated structures under changing external conditions. These difficulties make the development of a modulator / drainage agent system that achieves both ultra-low interfacial tension and good permeability and long-term stability an unsolved problem. Summary of the Invention

[0007] One objective of this invention is to provide an ultra-micro associative emulsion modifier to overcome the problems of poor oil displacement effect caused by insufficient reduction of interfacial tension, system instability, and insufficient deep migration ability of existing modifiers.

[0008] Another object of the present invention is to provide a method for preparing a modulating agent, so as to provide a standardized and repeatable mixing and post-processing process, and to establish basic process steps for obtaining a modulating agent product with qualified performance.

[0009] To address the aforementioned problems and achieve the objectives and other advantages of this invention, an ultrafine associative emulsion modulator is provided, comprising the following components in parts by weight: Water 0.40-0.70 parts, polyether-modified polysiloxane 0.15-0.25 parts, sodium α-olefin sulfonate 0.12-0.20 parts and sodium dodecyl sulfate 0.005-0.020 parts.

[0010] Preferably, the ultra-micro associative emulsion modifier further includes the following component in parts by weight: 0.10-0.20 parts of ethylene glycol.

[0011] Preferably, the ultrafine associative emulsion modifier further comprises the following components in parts by weight: Polyglycerol-6 didecanoate 0.005-0.020 parts, hydroxypropyl methylcellulose 0.001-0.008 parts, nano titanium dioxide 0.0005-0.003 parts, sodium citrate 0.001-0.005 parts.

[0012] A method for preparing an ultrafine associative emulsion modifier includes the following steps: 1) adding water to a preparation tank and adding other raw material components to the preparation tank, stirring and dissolving; 2) stirring the material evenly and then allowing it to settle; 3) taking samples for testing, and packaging and storing the qualified samples.

[0013] Preferably, in the preparation method of the ultrafine associative emulsion modifier, step 1) specifically includes the following steps: S1.1. Mix the first portion of water, which accounts for 10%-20% of the total water volume, with sodium chloride to prepare a sodium chloride solution with a mass concentration of 0.5%-2.0%. S1.2 Add sodium α-olefin sulfonate to the sodium chloride solution prepared in step S1.1, stir until completely dissolved, and let it stand at 25-40℃ for 0.5-2 hours to form an ion-controlled premixed solution; S1.3. Use the second portion of water, which accounts for 15%-25% of the total water volume, to dissolve the polyether-modified polysiloxane separately to form a polyether-modified polysiloxane premix. S1.4. Use the third portion of water, which accounts for 10%-20% of the total water volume, to dissolve sodium dodecyl sulfate separately to form a sodium dodecyl sulfate premixed solution; S1.5 Under stirring conditions, the sodium dodecyl sulfate premix obtained in step S1.4 is first added to the ion-regulating premix obtained in step S1.2 and mixed evenly to form an anionic composite premix. S1.6. While maintaining stirring, slowly and evenly add the polyether-modified polysiloxane premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes. S1.7 Finally, add the remaining equilibrium water to bring the system to the total water volume and total concentration specified in the formula.

[0014] Preferably, in the preparation method of the ultra-micro associative emulsion modifier, when preparing a modifier containing ethylene glycol, step S1.3 specifically involves: using a second portion of water accounting for 15%-25% of the total water volume to dissolve the polyether-modified polysiloxane and ethylene glycol together to form a siloxane-ethylene glycol premix; step S1.6 specifically involves: maintaining stirring, slowly and uniformly adding the siloxane-ethylene glycol premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes.

[0015] Preferably, in the preparation method of the ultrafine associative emulsion modifier, an online monitoring and intelligent control step is further included between step 1) and step 2): S1. Real-time acquisition of solution temperature T, conductivity K, and instantaneous power P of the stirring motor in the mixing system; and periodic sampling to measure the dynamic interfacial tension value γ of the mixing system; S2. Calculate the three process control indicators: Temperature deviation ΔT = T – T t T tThe preset process reference temperature; the rate of change of electrical conductivity K' = dK / dt; the cumulative stirring work E = ∫P(t)dt, with the integration interval from the stirring start time t0 in step 1) to the current time t; S3. Set and judge the following three conditions: Condition 1: Rate of change of conductivity K' ≤ K' th ;where K' th The threshold value for the rate of change of conductivity is a preset value used to determine that the dissolution and ion pre-assembly processes have become relatively stable. Condition 2: The dynamic interfacial tension value γ satisfies γ min ≤ γ ≤ γ max ;wherein γ min With γ max These are the lower and upper limits of the preset dynamic interfacial tension acceptable range, which are used to determine whether the system has reached the target interfacial activity. Condition 3: Cumulative stirring work E ≥ E th ; where E th This is a preset threshold for the cumulative stirring work used to determine whether the mixing system has obtained sufficient stirring energy; S4. When conditions 1, 2 and 3 are simultaneously met for the first time during the monitoring process, the dissolution and pre-assembly are determined to be complete, and then the process proceeds to step 2) for sedimentation. S5. If, starting from the stirring start time t0 in step 1), conditions 1, 2, and 3 are not simultaneously satisfied when the initial set time T1 is reached, then the following corresponding control operations will be performed based on the unsatisfied combination of conditions: S5.1 If condition one is not met, but conditions two and three are both met, then increase the stirring rate to 110%-130% of the current rate and set the first additional monitoring duration △t1. S5.2 If condition two is not satisfied, but conditions one and three are satisfied, then set a second additional stirring time Δt2, where Δt2 is 10-30 min; S5.3 If neither condition one nor condition two is satisfied, but condition three is satisfied, then perform the following operations in sequence: first increase the stirring rate to 110%-130% of the current rate, and then immediately set the second additional stirring time △t2. S5.4 If condition three is not met, but conditions one and two are met, and ΔT > 2℃, then the constant temperature control system is activated to adjust and maintain the temperature of the mixture at T. t Within the range of ± 1℃, and set the first additional monitoring duration △t1; S5.5 If condition three is not satisfied, but conditions one and two are satisfied, and ΔT ≤ 2℃, then increase the stirring rate to 110%-130% of the current rate, and set a third additional stirring time Δt3, where Δt3 is 10-30 min; S5.6 If neither condition 1 nor condition 3 is satisfied, but condition 2 is satisfied, then execute S5.1 first. After the first additional monitoring duration △t1 ends, if △T > 2℃, then execute S5.4; if △T ≤ 2℃, then execute S5.5. S5.7 If conditions two and three are not met, but condition one is met, then execute S5.2 first. After the second additional stirring time Δt2 ends, if ΔT > 2℃, then execute S5.4; if ΔT ≤ 2℃, then execute S5.5. S5.8 If conditions 1, 2, and 3 are not met, then proceed with S5.3 in sequence. After the second additional stirring time Δt2 ends, if ΔT > 2℃, proceed with S5.4; if ΔT ≤ 2℃, proceed with S5.5. S6. After executing any of the control operations in S5, continue monitoring and judgment within the corresponding additional time period; If conditions one, two, and three are simultaneously satisfied before the end of any additional time period, the dissolution and pre-assembly are deemed successful, and the process proceeds to step 2). If, starting from the stirring start time t0 in step 1), the accumulated time reaches the preset maximum total processing time T... max If conditions one, two, and three are still not met simultaneously, the batch is determined to be an abnormally mixed batch. Stirring is immediately stopped, the material in the current preparation tank is locked, and an audible and visual alarm is triggered, awaiting manual intervention.

[0016] Preferably, in the preparation method of the ultrafine associative emulsion modifier, the sedimentation step in step 2) specifically includes the following steps: S3.1 Real-time monitoring of the turbidity values ​​at least three preset height levels from top to bottom inside the settling tank, and simultaneous monitoring of the real-time turbidity and conductivity values ​​in the discharge pipeline at the bottom of the settling tank. S3.2 When the rate of change of real-time turbidity values ​​at all preset height levels is simultaneously lower than the first rate of change threshold, and the real-time turbidity value in the discharge pipeline at the bottom of the settling tank is lower than the first turbidity threshold, the system is determined to have reached the primary clarification state. S3.3. Upon reaching the initial clarification state, the stability assessment phase begins, during which the following monitoring is performed simultaneously: S3.3.1 Monitor the turbidity fluctuation range of the clear liquid layer at the top of the settling tank; the turbidity fluctuation range is obtained by recording the highest and lowest turbidity readings within a continuous monitoring cycle in this stage and calculating the difference between the two. S3.3.2 Monitor the real-time conductivity value in the discharge pipeline at the bottom of the settling tank and calculate its drift degree; the drift degree is the absolute percentage change of the real-time conductivity value relative to the initial conductivity value in this stage; S3.3.3 , By installing at least two temperature probes at different heights inside the settling tank, monitor and calculate the maximum temperature difference inside the settling tank; S3.4. When all of the following conditions are met simultaneously and maintained for a preset stabilization period, the settlement is deemed complete and the system reaches its final stable state: Condition A: The turbidity fluctuation of the clear liquid layer at the top of the settling tank is lower than the second turbidity threshold, and the second turbidity threshold is lower than the first turbidity threshold; Condition B: The drift of the real-time conductivity value in the discharge pipeline at the bottom of the settling tank is lower than the preset drift threshold; Condition C: The maximum temperature difference inside the settling tank is lower than the preset temperature uniformity threshold; S3.5 If the cumulative time since entering the initial clarification state exceeds the preset maximum stability assessment time t w If at least one of conditions A, B, and C is not met, the control procedure will be automatically initiated. The control procedure includes: starting the circulation pump to recirculate the material in the tank at a speed 30%-50% lower than the rated speed during the stirring operation in step 1), while simultaneously adjusting and maintaining the system temperature within the range of ±1℃ of the process reference temperature through the settling tank jacket; the control procedure will continue to be executed until conditions A, B, and C are simultaneously satisfied and the preset maximum stability assessment time t is maintained. w .

[0017] Preferably, in the preparation method of the ultra-micro associative emulsion modifier, step 3) includes the following specific steps: collecting a first finished product sample through a first automatic sampling valve set on the discharge pipeline of the settling tank, and collecting a second finished product sample through a second automatic sampling valve set before the inlet of the packaging unit; transporting the first finished product sample and the second finished product sample to the same or multiple analytical instruments for parallel testing; when the test results of the first finished product sample and the second finished product sample are consistent and both meet the preset qualified standards, the control system automatically authorizes the packaging unit to complete the packaging and warehousing of the current batch of products; when the test results of the first finished product sample and the second finished product sample are inconsistent, or any test result does not meet the preset qualified standards, the control system automatically locks the packaging unit and triggers an audible and visual alarm, while guiding the current batch of materials to an isolation storage tank.

[0018] Preferably, in the method for preparing the ultra-micro associative emulsion modifier, when preparing a modifier containing polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate, step S1.7 specifically includes the following steps: S1.7.1 Divide the balance water to be added into a fourth part and a fifth part, wherein the fourth part accounts for 30%-50% of the total balance water; S1.7.2. Use water from the fourth part, mix it with polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano titanium dioxide and sodium citrate, and disperse it at 1500-3000 rpm for 15-30 min using a high-speed disperser to form a composite synergistic dispersion. S1.7.3 Under the condition of maintaining stirring, add the composite synergistic dispersion obtained in step S1.7.2 to the mixture obtained in step S1.6; S1.7.4 Add water from the fifth part to bring the total water volume and total concentration of the system to the level specified in the formula.

[0019] The present invention has at least the following beneficial effects: This invention provides a composite system composed of water, polyether-modified polysiloxane, sodium α-olefin sulfonate, and sodium dodecyl sulfate in specific weight proportions. This system effectively solves the problems of insufficient interfacial activity, poor emulsion stability, and limited permeability in formation pores caused by improper surfactant formulation in existing oil recovery agents. Through molecular synergy and association among its components, this system can spontaneously form ultrafine and stable emulsion droplets, significantly reducing oil-water interfacial tension and enhancing the long-term stability of the system in complex formation environments, thereby improving oil recovery.

[0020] This invention further enhances the low-temperature adaptability and storage stability of the modulator by introducing ethylene glycol as an antifreeze and solubilizer. The addition of ethylene glycol not only effectively lowers the freezing point of the system, preventing freezing or demulsification in cold environments, but also promotes the uniform dispersion of components such as polyether-modified polysiloxanes, making the ultra-micro-associated emulsion structure more stable, thereby expanding the product's applicability and reliability under harsh climatic conditions.

[0021] This invention constructs a multi-scale synergistic system integrating interfacial strengthening, bulk stabilization, surface modification, and system integration by further introducing synergistic components such as polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate. Through multiple interactions with the base system, these components significantly enhance the density and elasticity of the interfacial film, improve the colloidal stability and shear resistance of the system, strengthen the hydrophilic modification effect on rock surfaces, and effectively alleviate the salting-out effect in high-salinity environments. This allows the modulator to maintain excellent overall performance even under harsh reservoir conditions such as high temperature and high salinity.

[0022] This invention provides a stepwise premixing and sequential assembly method for preparation. By precisely determining the amount of water used and controlling the mixing order and rate of key components, a simple physical mixing process is transformed into a controllable molecular assembly engineering process. This process guides surfactant molecules to assemble in an orderly manner, forming dense, uniformly sized ultrafine aggregates. This fundamentally improves the uniformity, stability, and batch consistency of the product, solving the problems of disordered molecular aggregation and large fluctuations in product performance in traditional one-time mixing processes.

[0023] This invention introduces an intelligent control method based on multi-parameter online monitoring and feedback. By real-time monitoring of solution temperature, conductivity change rate, cumulative stirring work, and dynamic interfacial tension, and by setting corresponding process control indicators and control strategies, it achieves a shift from "timed production" to "quality-controlled production." This method can dynamically determine and optimize the mixing and pre-assembly endpoints, automatically execute targeted control operations, significantly improve the reliability of the production process and the batch uniformity of product quality, and effectively overcome the performance inconsistencies caused by raw material or environmental fluctuations in traditional fixed processes.

[0024] This invention provides an intelligent sedimentation control method based on multi-parameter online monitoring. By real-time monitoring of turbidity values ​​at different heights within the sedimentation tank, the turbidity and conductivity of the bottom discharge, and combining this with monitoring of turbidity fluctuations, conductivity drift, and temperature differences within the tank during the stability assessment phase, the sedimentation endpoint can be objectively determined. This method not only accurately identifies when the system reaches the initial clarification state and the final stable state, but also possesses the ability to automatically initiate recirculation and temperature control, thereby ensuring that each batch of product forms a highly stable ultra-micro-associative structure and preventing the risk of performance degradation during storage.

[0025] This invention designs an online quality assessment and process control system based on dual-point automatic sampling and real-time parallel detection. Automatic sampling valves are installed at the discharge pipeline of the settling tank and the inlet of the packaging unit to collect two independent samples for parallel testing. When the test results of the two samples are consistent and meet the preset qualification standards, the system automatically authorizes packaging and warehousing; if the results are inconsistent or either sample fails, the system automatically locks the packaging unit, triggers an alarm, and isolates the material. This system achieves automated linkage between quality verification and the production process, effectively ensuring the reliability of the quality of outgoing products and establishing a rapid-response quality and safety interception mechanism.

[0026] The present invention provides a dedicated fine dispersion and integration process for complex systems containing synergistic components. By using a portion of the equilibrium water for high-speed dispersion pretreatment of polyglyceryl-6 dicaprate, hydroxypropyl methylcellulose, nano titanium dioxide, and sodium citrate, a uniform composite synergistic dispersion liquid is formed, which is then smoothly introduced into the assembled basic association system. This process ensures that each synergistic component is fully dissolved, dispersed, and uniformly integrated, maximizing their synergistic effects, solving the technical problems of uneven dispersion and easy agglomeration of multi-functional components in complex systems, and further improving the comprehensive performance and environmental adaptability of the displacement agent.

[0027] Other advantages, objectives, and features of the present invention will be partially reflected by the following description and partially understood by those skilled in the art through the research and practice of the present invention. Brief Description of the Drawings

[0028] Figure 1 It is a detection graph of the interfacial tension of an ultra-fine associated emulsion displacement agent brine solution with a mass concentration of 0.5%; Figure 2 It is a detection graph of the contact angle of an ultra-fine associated emulsion displacement agent aqueous solution with a mass concentration of 0.5%. Detailed Embodiments

[0029] The following further detailed description of the present invention is provided to enable those skilled in the art to implement it according to the text of the specification.

[0030] It should be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial sources unless otherwise specified.

[0031] The present invention provides an ultra-fine associated emulsion displacement agent, which includes the following components in parts by weight: 0.40 - 0.70 parts of water, 0.15 - 0.25 parts of polyether-modified polysiloxane, 0.12 - 0.20 parts of α-olefin sulfonate, and 0.005 - 0.020 parts of sodium dodecyl sulfate.

[0032] The closest prior art is the surfactant compounding system commonly used in oilfield chemical flooding operations, such as directly dissolving a single type of anionic surfactant such as α-olefin sulfonate or a small amount of alkyl sulfate in water for use. The main defect of such technical solutions is that there is a lack of effective and directional interaction design between different surfactant molecules, resulting in loose aggregate structures, large sizes, and high polydispersity in the solution. This makes the interfacial adsorption film insufficient in strength, and the interfacial tension can usually only be reduced to 10 -1The volume is on the order of mN / m. Meanwhile, the large micelle or droplet size, often exceeding 500 nm, severely restricts their effective injection and deep migration within the micropore throats of low-permeability reservoirs. Furthermore, the system, being a simple physical mixture, is thermodynamically unstable. Under long-term storage or conditions exceeding 80°C and high salinity, it is highly susceptible to component phase separation, active substance precipitation, or chemical degradation, leading to a sharp decline in oil displacement efficiency.

[0033] This solution provides an ultramicroemulsion modulator for directional association achieved through molecular design. The system comprises water, polyether-modified polysiloxane, sodium α-olefin sulfonate, and sodium dodecyl sulfate in precise weight ratios. The core design leverages the specific interactions between surfactant molecules with different structures to drive the spontaneous assembly of the system into a stable, nanoscale associative structure. Water (0.40-0.70 parts) serves as the solvent and continuous phase. Polyether-modified polysiloxane (0.15-0.25 parts) plays a crucial role; its hydrophobic polydimethylsiloxane segments tend to insert into the oil phase or aggregate at the interface, while the hydrophilic polyether segments extend into the aqueous phase. This structure results in extremely high interfacial adsorption efficiency and extremely low interfacial energy, forming the cornerstone for achieving ultra-low interfacial tension. Sodium α-olefin sulfonate (0.12-0.20 parts) serves as the main anionic surfactant. Its long-chain alkyl hydrophobic tail chain can bind with the siloxane segments of the polyether-modified polysiloxane through hydrophobic interactions, while its hydrophilic head group provides strong hydration and electrostatic repulsion, endowing the entire composite system with good water solubility and salt resistance. The introduction of trace amounts of sodium dodecyl sulfate (SDS) plays a crucial role. Although both SDS and sodium α-olefin sulfonate (AOS) are anionic surfactants, SDS has a higher head group charge density and a more compact molecular conformation. This effectively regulates the arrangement of AOS and polyether-modified polysiloxane in mixed micelles or interfacial films, promoting a more compact and ordered molecular arrangement, thereby reducing interfacial tension and improving the density and stability of the interfacial film. This densification significantly reduces the size of the associative aggregate and improves its uniformity and stability. It is through the aforementioned molecular synergistic mechanism—the powerful tension-reducing effect of long-chain siloxanes, the emulsification and salt resistance of long-chain olefin sulfonates, and the dense filling effect of short-chain sulfates—that the components spontaneously associate in aqueous solution at specific ratios, forming a thermodynamically stable, nanoscale particle size distribution with extremely low polydispersity ultrafine associative emulsion. This structural characteristic is the fundamental reason why this solution can simultaneously achieve ultra-low interfacial tension, excellent temperature and salt resistance, and good deep penetration capability.

[0034] Example 1 The following raw materials were weighed to prepare one ton of product: 0.614 t of water, 0.203 t of polyether-modified polysiloxane (BYK-348), 0.170 t of sodium α-olefin sulfonate (AOS-14), and 0.013 t of sodium dodecyl sulfate. All the water was added to a mixing tank, and stirring was started at a speed of 100 r / min. The weighed polyether-modified polysiloxane, sodium α-olefin sulfonate, and sodium dodecyl sulfate were added to the tank sequentially, and stirring was continued for 3 hours until all components were completely dissolved and the system was homogeneous. Stirring was stopped, and the mixture was allowed to settle for 24 hours to obtain the finished ultra-micro associative emulsion modifier. The product was then subjected to comprehensive performance characterization.

[0035] Detailed test of oil washing ability: This experiment aims to evaluate the stripping efficiency of the modifier on attached crude oil. The specific steps are as follows: A clean steel sheet is weighed (weight recorded as W0), completely immersed in the target crude oil, and aged in a constant temperature oven at 60℃ (reservoir temperature) for 48 hours. After removal, excess crude oil dripping from the edge of the steel sheet is carefully scraped off, and the total weight of the oil-coated steel sheet is weighed (recorded as W1). Subsequently, the oil-coated steel sheet is immersed in a container containing a 0.5% mass fraction of the test solution (prepared from the finished product and pure water), and statically soaked at 60℃ for 12 hours. After removal, the surface of the steel sheet is gently rinsed with deionized water, dried, and weighed (recorded as W2). The oil washing rate is calculated using the formula: [(W1-W2) / (W1-W0)] × 100%. As a blank control, the same experiment is performed using standard saline. The results of the oil washing experiment are shown in Table 1. The comprehensive performance evaluation results are shown in Table 2. Figure 1 and Figure 2 These are the interfacial tension and contact angle test results, respectively.

[0036] Comparative Example 1 A comparative solution was prepared according to the following parts by weight: 0.80 parts water and 0.20 parts sodium α-olefin sulfonate (AOS-14). Sodium α-olefin sulfonate was added to water and stirred at 100 r / min for 2 h until completely dissolved. The solution was then allowed to stand for 24 h to settle, yielding the comparative product.

[0037] Table 1 Results of the oil washing experiment

[0038] Table 1 provides a clear overview of the core application efficiency of the modifier in this solution. The finished solution in Example 1 achieved an oil washing rate of 81.54%, representing a 46.28 percentage point increase compared to the standard brine used as a blank control. This significant improvement directly demonstrates the powerful emulsifying and stripping ability of this composite system. In contrast, Comparative Example 1, using only sodium α-olefin sulfonate, achieved an oil washing rate of 48.23%, showing a limited improvement. A comprehensive comparison reveals that the oil washing efficiency of this multi-component synergistic system is far superior to that of single-component systems and systems without an active medium.

[0039] Table 2 Comprehensive Performance Evaluation Results

[0040] Table 2 systematically describes the mechanism, structural basis, and environmental adaptability of the proposed modulator for achieving high performance, as detailed below: Regarding interfacial activity, Example 1 achieved 2.05 × 10⁻⁶ under simulated formation water conditions. -2 The ultra-low interfacial tension is mN / m, compared to 5.6×10 in Comparative Example 1. -2 The mN / m ratio is more than an order of magnitude lower. This directly confirms that a significant synergistic tension-reducing effect occurs between the polyether-modified polysiloxane and the anionic surfactant, which is a core indicator for achieving high-efficiency oil displacement capability.

[0041] Regarding wetting modification, Example 1 showed a contact angle as low as 20.71°, indicating that it could strongly reverse the rock surface from an oil-wet state to a water-wet state, which is beneficial for displacing the water film and spreading, thereby macroscopically promoting crude oil flow. Comparative Example 1 had a contact angle of 65.3°, still in an intermediate wetting state, and its modification ability was significantly insufficient.

[0042] Regarding the microstructure, Example 1 exhibits an average particle size D50 of 85 nm and a polydispersity index (PDI) of 0.15. These two figures provide quantitative evidence for the concepts of "ultramicro" and "association." The 85 nm nanoscale ensures that the system can smoothly enter and act on the micropores and throats of the reservoir; the low PDI value of 0.15 indicates that the aggregates formed in the system are highly uniform in size, reflecting the orderliness and stability of the molecular assembly process. Comparative Example 1 has a D50 of 520 nm and a PDI of 0.45, indicating that its aggregates are large and widely distributed, falling within the category of conventional micelles or coarse emulsions.

[0043] Regarding thermal stability, the finished product of Example 1, after being aged at 120°C, exhibited an interfacial tension of 3.1 × 10⁻⁶ at 90°C. -2 mN / m, still at 10 -2 The mN / m order of magnitude indicates that the system retains good interfacial activity under high-temperature conditions, meeting the basic requirements for thermal stability in oilfields, and the solution has a uniform appearance. This demonstrates that its ultra-micro-associative structure has high thermodynamic stability, and the active components have not undergone significant degradation or aggregation. In contrast, Comparative Example 1 showed a significant increase in interfacial tension and turbidity after aging, indicating that the single-component system cannot withstand high temperatures.

[0044] Regarding salt tolerance, Example 1 maintained uniform transparency and an interfacial tension of 2.8 × 10⁻⁶ even at a high salinity of 80,000 mg / L. -2The mN / m ratio indicates that the system exhibits excellent salt resistance. This is because the polyether segments of the polyether-modified polysiloxane possess good hydration capabilities, maintaining the extended state of the molecular chains in high-salt environments and inhibiting the salting-out behavior of anionic surfactants through steric hindrance. Simultaneously, the hydrophobic siloxane segments form mixed micelles with sodium α-olefin sulfonate and sodium dodecyl sulfate, enhancing the salt resistance of the micelles and enabling the system to maintain ultra-low interfacial tension even at high salinity. Comparative Example 1, on the other hand, immediately destabilizes under high salt conditions and fails to form an effective active system.

[0045] Regarding long-term storage performance, the product in Example 1 showed minimal performance change after standing for 90 days, confirming that the ultra-micro associative emulsion has excellent kinetic stability at room temperature, meeting the storage and transportation requirements of industrial products.

[0046] In summary, from practical application effects, intrinsic mechanism of action, microstructural characteristics to long-term environmental stability, the ultra-micro associative emulsion modifier provided in this solution has been fully demonstrated to achieve a significant improvement in comprehensive performance through precise component selection and ratio design, effectively solving the key defects of existing technologies in terms of interfacial activity, system stability and reservoir adaptability.

[0047] In another embodiment, the ultra-micro associative emulsion modifier further includes the following component in parts by weight: 0.10-0.20 parts of ethylene glycol.

[0048] Ethylene glycol was further added to the quaternary composite system. The main effect of ethylene glycol is to effectively improve the system's low-temperature adaptability. As an antifreeze agent, ethylene glycol significantly lowers the system's freezing point, preventing freezing or demulsification during low-temperature storage and transportation, thus ensuring long-term stability in cold environments. Simultaneously, the addition of ethylene glycol also helps promote the dissolution and dispersion of each component, especially the polyether-modified polysiloxane, making it easier for the mixture to form a uniform and stable ultra-micro-associated emulsion structure. This further expands the product's applicability and reliability in extremely cold climates while maintaining all the performance characteristics of the basic formulation.

[0049] In another embodiment, the ultrafine associative emulsion modifier further includes the following components in parts by weight: Polyglycerol-6 didecanoate 0.005-0.020 parts, hydroxypropyl methylcellulose 0.001-0.008 parts, nano titanium dioxide 0.0005-0.003 parts, sodium citrate 0.001-0.005 parts.

[0050] In the ultra-micro associative emulsion modulator system, polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano titanium dioxide and sodium citrate are added. These components produce multiple synergistic effects with the basic components, thereby systematically improving the overall performance of the modulator.

[0051] Polyglycerol-6 didecanoate undergoes synergistic adsorption at the interface with polyether-modified polysiloxane and sodium α-olefin sulfonate. Its branched hydrophilic head groups bind to the polar groups of the latter two via hydrogen bonds, while its hydrophobic chains interact with them hydrophobically. This process strengthens the interfacial film structure, making it denser and tougher, thus significantly enhancing the stability and elasticity of the interfacial film. The effect is that the oil-water interfacial tension can reach and be maintained at an ultra-low level for a long period, and the resistance to high temperatures and shear failure is greatly improved.

[0052] Hydroxypropyl methylcellulose (HPMC) acts as a steric stabilizer in the aqueous phase, increasing system viscosity and inhibiting the aggregation of nanoassemblies. Its molecular chains interact weakly with the polyether segments of polyether-modified polysiloxanes and the hydroxyl groups of polyglycerol esters through hydrogen bonds, further enhancing the colloidal stability of the system. This interaction couples interfacial stability with the rheological properties of the aqueous phase. The result is a significant improvement in the macroscopic viscosity and colloidal stability of the system, ensuring that the product remains homogeneous and does not undergo stratification or precipitation during long-term storage and at high temperatures.

[0053] Hydrophilic nano-titanium dioxide plays a role at interfaces and on rock surfaces. At the interface, its particles synergistically enhance emulsion stability through steric hindrance with anionic surfactants such as sodium dodecyl sulfate. On the rock surface, its particles synergistically adsorb with surfactant molecules such as polyether-modified polysiloxanes, achieving nanoscale modification of the rock surface. The effect is a significant enhancement and persistence of the hydrophilic modification of the rock surface, thereby substantially improving crude oil stripping efficiency.

[0054] Sodium citrate plays a crucial role in ion regulation and bridging within the system. Its sodium ions modulate the electrical double layer of anionic surfactants, promoting a more compact arrangement. Its citrate ions act as hydrogen bond nodes, forming a broad dynamic network with hydroxypropyl methylcellulose, polyglycerol esters, and water molecules. This effect balances the electrochemical environment of the system and enhances component compatibility. Ultimately, it effectively mitigates the salting-out effect of surfactants in high-mineralization environments, ensuring the overall stability and functional integrity of the complex system under harsh conditions.

[0055] Therefore, these new components, through multi-scale interactions with the basic system, jointly construct a synergistic system encompassing interface strengthening, bulk phase locking, surface modification, and system integration. This system enables the flood control agent to maintain its core function of ultra-low interfacial tension while achieving excellent long-term stability, deep oil washing capability, and broad environmental adaptability, thus enabling its reliable application in complex and demanding reservoirs such as those with high temperature and high salinity.

[0056] A method for preparing an ultrafine associative emulsion modifier includes the following steps: 1) Add water to a preparation tank and add other raw material components to the preparation tank, and stir to dissolve; stirring is done by stirring with a mixer for 2-3 hours or by circulating with a circulating pump for 8 hours; 2) After the material is stirred evenly, allow it to settle for 20-30 hours; 3) Take samples for testing, and package and store them after they pass the test.

[0057] In another embodiment, the preparation method of the ultrafine associative emulsion modifier includes, in step 1), the following steps: S1.1. Mix the first portion of water, which accounts for 10%-20% of the total water volume, with sodium chloride to prepare a sodium chloride solution with a mass concentration of 0.5%-2.0%. S1.2 Add sodium α-olefin sulfonate to the sodium chloride solution prepared in step S1.1, stir until completely dissolved, and let it stand at 25-40℃ for 0.5-2 hours to form an ion-controlled premixed solution; S1.3. Use the second portion of water, which accounts for 15%-25% of the total water volume, to dissolve the polyether-modified polysiloxane separately to form a polyether-modified polysiloxane premix. S1.4. Use the third portion of water, which accounts for 10%-20% of the total water volume, to dissolve sodium dodecyl sulfate separately to form a sodium dodecyl sulfate premixed solution; S1.5 Under stirring conditions, the sodium dodecyl sulfate premix obtained in step S1.4 is first added to the ion-regulating premix obtained in step S1.2 and mixed evenly to form an anionic composite premix. S1.6. While maintaining stirring, slowly and evenly add the polyether-modified polysiloxane premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes. S1.7 Finally, add the remaining equilibrium water to bring the system to the total water volume and total concentration specified in the formula.

[0058] Compared to the problems of disordered molecular aggregation, poor product uniformity, and batch stability caused by one-time mixing in basic formulations, this solution provides a systematic stepwise premixing and sequential assembly process. It aims to transform a simple physical mixing process into a controllable molecular assembly engineering process by precisely dividing and functionally allocating the total water volume and strictly controlling the mixing order and rate of key components. This guides the orderly assembly of surfactant molecules to form dense and uniformly sized ultra-micro associative compounds, fundamentally improving product uniformity and batch stability.

[0059] The first step involves preparing a 0.5%-2.0% sodium chloride solution using 10%-20% water to create a specific weak electrolyte environment. Sodium α-olefin sulfonate is then added to this salt solution and allowed to mature at 25-40°C for 0.5-2 hours. This maturation process allows the sodium α-olefin sulfonate molecules to pre-assemble under ion regulation, forming a more stable ion-regulated premixed solution, which serves as a template for subsequent ordered molecular assembly.

[0060] The second step involves using an additional 15%-25% of the total water volume to dissolve the polyether-modified polysiloxane separately, forming a premixed polyether-modified polysiloxane solution. This isolation process aims to prevent the polyether-modified polysiloxane from directly contacting the high concentration of anionic surfactants in the initial stage, avoiding the formation of uneven, coarse aggregates due to differences in charge or solubility, and ensuring that its molecular chains can fully extend.

[0061] The third step involves using an additional 10%-20% of the total water volume to dissolve sodium dodecyl sulfate separately, forming a separate sodium dodecyl sulfate premix. Under stirring conditions, this sodium dodecyl sulfate premix is ​​first added to the aforementioned matured ion-regulated premix to form an anionic composite premix. This sequence of operations aims to allow trace amounts of sodium dodecyl sulfate to preferentially bind with the partially structured α-olefin sulfonate molecules, thereby further optimizing and stabilizing the internal structure of the anionic surfactant complex.

[0062] The fourth step is the core of the entire process control: under continuous stirring, the polyether-modified polysiloxane premix is ​​slowly and uniformly added dropwise to the above-mentioned anionic composite premix, with the addition time strictly controlled within 30-60 minutes. The purpose of slow addition is to effectively control the binding kinetics between the nonionic and ionic surfactants, guiding them to undergo gradual and orderly molecular assembly, thereby spontaneously forming dense, small-sized, and uniformly distributed ultramicro-associations.

[0063] Finally, the remaining equilibrium water is added to adjust the entire system to the total concentration specified in the formulation. Through these interconnected steps, this process transforms a simple physical mixing process into a controllable molecular assembly engineering process.

[0064] Example 2 The following raw materials were weighed to prepare one ton of product: 0.614 t of water, 0.203 t of polyether-modified polysiloxane, 0.170 t of sodium α-olefin sulfonate, and 0.013 t of sodium dodecyl sulfate. A stepwise premixing and sequential assembly process was used. First, 15% of the total water volume was mixed with sodium chloride to prepare a 1.0% sodium chloride solution. Sodium α-olefin sulfonate was added and stirred until dissolved, then allowed to stand at 30°C for 1 hour to form an ion-controlled premix. 20% of the total water volume was used to dissolve the polyether-modified polysiloxane separately to form a polyether-modified polysiloxane premix. Sodium dodecyl sulfate was separately dissolved in 15% of the total water volume to form a sodium dodecyl sulfate premix. The sodium dodecyl sulfate premix was first added to the ion-controlled premix under stirring and mixed thoroughly. Then, the polyether-modified polysiloxane premix was slowly added over 40 minutes. Finally, the remaining water was added to balance to the total concentration. The mixture was allowed to settle for 24 hours to obtain the final product. The performance comparison results between Example 2 (stepwise sequential assembly method) and Example 1 (one-time mixing method) are shown in Table 3.

[0065] Table 3 Performance Comparison Results of Example 2 and Example 1

[0066] In summary, compared to the one-time mixing method in Example 1, the stepwise premixing and sequential assembly process used in Example 2 demonstrates comprehensive and significant improvements in all key performance indicators, including washing efficiency, interfacial activity, wetting modification ability, microstructure uniformity, temperature resistance, salt resistance, and long-term stability. This process, through precise ionic environment control and stepwise sequential mixing, effectively guides the orderly assembly of different surfactant molecules, forming smaller, narrower-distribution, and more structurally stable ultra-micro nano-associations. This completely solves the core technical challenges of disordered molecular aggregation and poor batch-to-batch stability in the preparation of basic formulations.

[0067] In another embodiment, in the preparation method of the ultra-micro associative emulsion modifier, when preparing a modifier containing ethylene glycol, step S1.3 specifically involves: using a second portion of water accounting for 15%-25% of the total water volume to dissolve the polyether-modified polysiloxane and ethylene glycol together to form a siloxane-ethylene glycol premix; step S1.6 specifically involves: maintaining stirring, slowly and uniformly adding the siloxane-ethylene glycol premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes.

[0068] By pre-dissolving ethylene glycol and polyether-modified polysiloxane to form a homogeneous premix, the dispersion and dissolution efficiency of polyether-modified polysiloxane in the aqueous phase is significantly improved, effectively preventing local aggregation that may occur when treated alone. Furthermore, the antifreeze and solubilizing effects of ethylene glycol are more uniformly applied to the polysiloxane segments at the molecular scale. This further promotes the formation of an ordered and dense ultra-micro-associative structure during the subsequent key assembly process with the anionic composite premix. Ultimately, while ensuring the core interfacial activity of the modulator, the product's storage stability and antifreeze performance under low-temperature conditions are significantly enhanced.

[0069] In another embodiment, the preparation method of the ultrafine associative emulsion modulator includes an online monitoring and intelligent control step between step 1) and step 2). S1. Real-time acquisition of solution temperature T, conductivity K, and instantaneous power P of the stirring motor in the mixing system; and periodic sampling to measure the dynamic interfacial tension value γ of the mixing system; S2. Calculate the three process control indicators: Temperature deviation ΔT = T – T t T t The preset process reference temperature; the rate of change of electrical conductivity K' = dK / dt; the cumulative stirring work E = ∫P(t)dt, with the integration interval from the stirring start time t0 in step 1) to the current time t; S3. Set and judge the following three conditions: Condition 1: Rate of change of conductivity K' ≤ K' th ;where K' th The threshold value for the rate of change of conductivity is a preset value used to determine that the dissolution and ion pre-assembly processes have become relatively stable. Condition 2: The dynamic interfacial tension value γ satisfies γ min ≤ γ ≤ γ max ;wherein γ min With γ max These are the lower and upper limits of the preset dynamic interfacial tension acceptable range, which are used to determine whether the system has reached the target interfacial activity. Condition 3: Cumulative stirring work E ≥ E th ; where E th This is a preset threshold for the cumulative stirring work used to determine whether the mixing system has obtained sufficient stirring energy; S4. When conditions 1, 2 and 3 are simultaneously met for the first time during the monitoring process, the dissolution and pre-assembly are determined to be complete, and then the process proceeds to step 2) for sedimentation. S5. If, starting from the stirring start time t0 in step 1), conditions 1, 2, and 3 are not simultaneously satisfied when the initial set time T1 is reached, then the following corresponding control operations will be performed based on the unsatisfied combination of conditions: S5.1 If condition one is not met, but conditions two and three are both met, then increase the stirring rate to 110%-130% of the current rate and set the first additional monitoring duration △t1. S5.2 If condition two is not satisfied, but conditions one and three are satisfied, then set a second additional stirring time Δt2, where Δt2 is 10-30 min; S5.3 If neither condition one nor condition two is satisfied, but condition three is satisfied, then perform the following operations in sequence: first increase the stirring rate to 110%-130% of the current rate, and then immediately set the second additional stirring time △t2. S5.4 If condition three is not met, but conditions one and two are met, and ΔT > 2℃, then the constant temperature control system is activated to adjust and maintain the temperature of the mixture at T. t Within the range of ± 1℃, and set the first additional monitoring duration △t1; S5.5 If condition three is not satisfied, but conditions one and two are satisfied, and ΔT ≤ 2℃, then increase the stirring rate to 110%-130% of the current rate, and set a third additional stirring time Δt3, where Δt3 is 10-30 min; S5.6 If neither condition 1 nor condition 3 is satisfied, but condition 2 is satisfied, then execute S5.1 first. After the first additional monitoring duration △t1 ends, if △T > 2℃, then execute S5.4; if △T ≤ 2℃, then execute S5.5. S5.7 If conditions two and three are not met, but condition one is met, then execute S5.2 first. After the second additional stirring time Δt2 ends, if ΔT > 2℃, then execute S5.4; if ΔT ≤ 2℃, then execute S5.5. S5.8 If conditions 1, 2, and 3 are not met, then proceed with S5.3 in sequence. After the second additional stirring time Δt2 ends, if ΔT > 2℃, proceed with S5.4; if ΔT ≤ 2℃, proceed with S5.5. S6. After executing any of the control operations in S5, continue monitoring and judgment within the corresponding additional time period; If conditions one, two, and three are simultaneously satisfied before the end of any additional time period, the dissolution and pre-assembly are deemed successful, and the process proceeds to step 2). If, starting from the stirring start time t0 in step 1), the accumulated time reaches the preset maximum total processing time T... max If conditions one, two, and three are still not met simultaneously, the batch is determined to be an abnormally mixed batch. Stirring is immediately stopped, the material in the current preparation tank is locked, and an audible and visual alarm is triggered, awaiting manual intervention.

[0070] To address the issues of uneven mixing, inadequate pre-assembly, and large batch-to-batch performance fluctuations that arise from reliance on fixed process times and manual judgment during the preparation of ultrafine associative emulsion modifiers, this solution introduces an intelligent control method based on multi-parameter online monitoring and feedback. This method aims to dynamically determine and optimize the mixing and pre-assembly endpoints through real-time, objective process indicators, thereby ensuring that each batch of product achieves consistent and excellent performance.

[0071] Specifically, this method first acquires key process parameters of the mixing system in real time: solution temperature T, conductivity K, and instantaneous power P of the stirring motor. It also periodically samples and measures the dynamic interfacial tension value γ, which directly reflects the core function of the product. Production is guided by the calculation and judgment of these parameters: Temperature deviation ΔT = T – T t (T) t The preset process reference temperature is used to monitor the temperature control accuracy of the system; the conductivity change rate K' = dK / dt is calculated to characterize the dynamic stability of the ion dissolution and molecular pre-assembly process. When the change rate is lower than the preset threshold K', th When the ionic energy is 0.01 μS / (cm·s), the ionic environment can be considered to be stable. The cumulative stirring work E = ∫P(t)dt from the start of stirring to the current time t is calculated to quantify whether the mechanical energy input to the system is sufficient. Its value must reach a preset threshold E. th (e.g., 800 kJ). Simultaneously, the directly monitored dynamic interfacial tension γ must fall within a preset acceptable range (e.g., γ...). min 1.5×10 -2 mN / m, γ max 3.0×10 -2 (mN / m) is the most direct basis for determining whether the system has formed a molecular structure with the target interface activity.

[0072] The core logic of this intelligent control process is as follows: when the three conditions—stable conductivity (condition 1), satisfactory interfacial activity (condition 2), and sufficient stirring energy input (condition 3)—are simultaneously met for the first time, the system determines that dissolution and pre-assembly are complete and immediately proceeds to the sedimentation step, thus realizing the transition from timed production to quality-controlled production. If the conditions are not simultaneously met within the set initial time T1 (e.g., 30 minutes), the system will automatically execute corresponding control strategies based on which condition(s) are not met. For example, if the conductivity change is not yet stable (condition 1 is not met) but the interfacial activity and stirring energy are satisfactory, the stirring rate will be automatically increased to promote mixing; if the interfacial activity is not satisfactory (condition 2 is not met) but other conditions are met, the stirring time will be automatically extended; if the temperature deviation is too large and affects the satisfaction of condition 3, the temperature control system will be activated for adjustment. These control operations are designed to specifically address the bottleneck problem in the current mixing stage. If additional control is applied, the total processing time will be increased to the maximum set limit T. max If all conditions are met within 120 minutes (e.g., T), qualified products can still be produced; if the time exceeds T... max If the requirements still cannot be met, the batch is automatically identified as abnormal and an alarm is triggered to prevent defective products from entering subsequent processes. This solution effectively solves the problem of inconsistent batch performance caused by minor fluctuations in raw materials or environmental changes in traditional fixed processes through real-time monitoring, automatic judgment, and intelligent feedback control, significantly improving the reliability of the production process and the uniformity of product quality.

[0073] Example 3 The following raw materials were weighed to prepare one ton of product: 0.614t of water, 0.203t of polyether-modified polysiloxane, 0.170t of sodium α-olefin sulfonate, and 0.013t of sodium dodecyl sulfate. Online monitoring and intelligent control were applied during the preparation process. All water was added to the preparation tank, stirring was started, and each raw material component was added sequentially.

[0074] The system's preset key parameter is: process reference temperature T. t At 35℃, the threshold for the rate of change of conductivity is K'. th The lower limit of the acceptable range for dynamic interfacial tension is 0.01 μS / cm·s. min 1.5×10 -2 mN / m, upper limit γ max 3.0×10 -2 mN / m, cumulative stirring work threshold E th The power is 800 kJ. The initial processing time T1 is set to 30 minutes, and the maximum total processing time T is [not specified]. max It takes 120 minutes.

[0075] After production starts, the system acquires the solution temperature T, conductivity K, and instantaneous power P of the stirring motor in real time, and automatically samples and measures the dynamic interfacial tension γ of the mixture every 10 minutes. At the end of the initial set time T1, the system determines: Condition 1 (conductivity change rate K' ≤ K') th Condition 1 is not satisfied; condition 2 (dynamic interfacial tension value γ satisfies γ) is not satisfied. min ≤γ ≤ γ max Condition 3 (cumulative stirring work E ≥ E) is not met. th Conditions 1, 2, and 3 are not met simultaneously. Since the temperature deviation ΔT is 1℃ (ΔT≤2℃), according to S5.8, the system executes the control operation specified in S5.8: S5.3 is executed sequentially, first increasing the stirring rate to 120% of the current rate, and then immediately setting the second additional stirring duration Δt2 to 20 minutes. At the end of the second additional stirring duration Δt2, the system determines that conditions 1, 2, and 3 are still not simultaneously met. Since the system detects that the temperature deviation ΔT is still 1℃ (ΔT≤2℃), according to S5.8, the system then executes S5.5, which again increases the stirring rate to 120% of the current rate and sets the third additional stirring duration Δt3 to 15 minutes.

[0076] During the third additional stirring time Δt3, the system was continuously monitored. At a cumulative stirring time of 52 min, the system recorded: the rate of change of conductivity K' was 0.008 μS / cm·s (satisfying condition one); the dynamic interfacial tension value γ was 1.95 × 10⁻⁶. -2 mN / m (condition two is met); cumulative stirring work E is 805kJ (condition three is met). When all three conditions are met simultaneously for the first time, the system determines that dissolution and pre-assembly are complete, and then automatically stops stirring and proceeds to the sedimentation step. The mixture is allowed to settle for 24 hours to obtain the final product. The performance comparison results between Example 3 (online monitoring and intelligent control method) and Example 1 (one-time mixing method) are shown in Table 4.

[0077] Table 4 Performance Comparison Results of Example 3 and Example 1

[0078]

[0079] In summary, compared to the one-time, fixed-duration mixing process of Example 1, the online monitoring and intelligent control method used in Example 3 shows significant improvements in all key performance indicators, including washing efficiency, interfacial activity, wetting modification ability, and microstructure uniformity, while maintaining excellent thermal and storage stability. This intelligent process, by replacing fixed-duration, experience-based production with a production method focused on achieving quality standards, significantly enhances the reliability of the production process and the batch-to-batch uniformity of product quality, effectively solving the inherent problems of traditional methods. However, the performance improvement of Example 3 mainly stems from the optimized control of mixing process parameters, ensuring that the potential of the predetermined formulation is fully realized. The superior overall performance exhibited by Example 2 is fundamentally due to the use of a more fundamental stepwise sequential assembly process. This process actively guides and reconstructs the microscopic process of molecular assembly by precisely designing the paths and sequences of molecular interactions, thereby forming a more stable and denser nano-associative structure thermodynamically. Therefore, the optimization of Example 3 is an improvement in efficiency and consistency within the existing mixing framework, while Example 2 achieves structural innovation at the level of molecular assembly principles, making it more advantageous in terms of extreme performance.

[0080] In another embodiment, the sedimentation step in step 2) of the preparation method of the ultrafine associative emulsion modifier specifically includes the following steps: S3.1 Real-time monitoring of the turbidity values ​​at least three preset height levels from top to bottom inside the settling tank, and simultaneous monitoring of the real-time turbidity and conductivity values ​​in the discharge pipeline at the bottom of the settling tank. S3.2 When the rate of change of real-time turbidity values ​​at all preset height levels is simultaneously lower than the first rate of change threshold, and the real-time turbidity value in the discharge pipeline at the bottom of the settling tank is lower than the first turbidity threshold, the system is determined to have reached the primary clarification state. S3.3. Upon reaching the initial clarification state, the stability assessment phase begins, during which the following monitoring is performed simultaneously: S3.3.1 Monitor the turbidity fluctuation range of the clear liquid layer at the top of the settling tank; the turbidity fluctuation range is obtained by recording the highest and lowest turbidity readings within a continuous monitoring cycle in this stage and calculating the difference between the two. S3.3.2 Monitor the real-time conductivity value in the discharge pipeline at the bottom of the settling tank and calculate its drift degree; the drift degree is the absolute percentage change of the real-time conductivity value relative to the initial conductivity value in this stage; S3.3.3 , By installing at least two temperature probes at different heights inside the settling tank, monitor and calculate the maximum temperature difference inside the settling tank; S3.4. When all of the following conditions are met simultaneously and maintained for a preset stabilization period, the settlement is deemed complete and the system reaches its final stable state: Condition A: The turbidity fluctuation of the clear liquid layer at the top of the settling tank is lower than the second turbidity threshold, and the second turbidity threshold is lower than the first turbidity threshold; Condition B: The drift of the real-time conductivity value in the discharge pipeline at the bottom of the settling tank is lower than the preset drift threshold; Condition C: The maximum temperature difference inside the settling tank is lower than the preset temperature uniformity threshold; S3.5 If the cumulative time since entering the initial clarification state exceeds the preset maximum stability assessment time t w If at least one of conditions A, B, and C is not met, the control procedure will be automatically initiated. The control procedure includes: starting the circulation pump to recirculate the material in the tank at a speed 30%-50% lower than the rated speed during the stirring operation in step 1), while simultaneously adjusting and maintaining the system temperature within the range of ±1℃ of the process reference temperature through the settling tank jacket; the control procedure will continue to be executed until conditions A, B, and C are simultaneously satisfied and the preset maximum stability assessment time t is maintained. w .

[0081] To address the issues of sedimentation control agents relying on fixed time intervals during the sedimentation process, making it impossible to determine in real time whether the system has reached a truly stable state, and the difficulty in preventing product stratification or performance inconsistencies due to uneven temperature or fine aggregates, this solution provides an intelligent sedimentation control method based on multi-parameter online monitoring. This method aims to objectively determine the sedimentation endpoint through real-time, multi-dimensional data feedback and possesses automatic adjustment capabilities, thereby ensuring that each batch of product forms a highly stable ultra-micro-associative structure.

[0082] This method first monitors the real-time turbidity values ​​at at least three preset height levels from top to bottom within the settling tank, and simultaneously monitors the real-time turbidity and conductivity values ​​in the bottom discharge pipeline of the settling tank. The aim is to comprehensively capture the clarification process of the system from both spatial distribution and outlet quality dimensions. When the rate of change of real-time turbidity values ​​at all preset height levels is simultaneously lower than a first rate of change threshold, and the turbidity value of the bottom discharge is also lower than the first turbidity threshold, the system is considered to have reached a preliminary clarification state. Here, the first rate of change threshold is a preset upper limit value for the rate of turbidity change, for example, a decrease of no more than 5 NTU per hour, used to determine that the turbidity changes at each level have tended to stabilize, indicating that the settling process of large particle aggregates is basically complete; the first turbidity threshold is a preset upper limit value for the absolute turbidity, for example, 10 NTU, used to determine that the macroscopic clarity of the bottom discharge fluid has initially met the standard. The effect of this step is to accurately identify the key turning point where large particle aggregates have basically completed settling, replacing a rough judgment based solely on experience and time.

[0083] Upon reaching the initial clarification state, the system enters a more refined stability assessment phase. This phase involves three monitoring operations: First, monitoring the turbidity fluctuations of the clear liquid layer at the top of the settling tank, quantifying the microscopic uniformity of the clear liquid layer by calculating the difference between the highest and lowest turbidity values ​​over a continuous monitoring period. Second, monitoring the real-time conductivity value in the discharge pipeline at the bottom of the settling tank, and calculating its absolute percentage change relative to the initial value of this phase, i.e., the degree of drift, to determine whether the distribution of ions and charged colloidal components in the system has reached dynamic equilibrium. Third, monitoring the maximum temperature difference inside the settling tank using temperature probes at at least two different heights to assess the thermal uniformity of the system. The purpose of these three monitoring operations is to comprehensively evaluate the internal equilibrium state of the ultrafine associative system from three core levels: colloidal stability, electrochemical stability, and thermal stability.

[0084] When three conditions are simultaneously met and maintained for a preset stabilization period—the turbidity fluctuation of the top clear liquid layer being lower than the second turbidity threshold, the conductivity drift at the bottom being lower than the preset drift threshold, and the maximum temperature difference within the tank being lower than the preset temperature uniformity threshold—the system determines that sedimentation is complete and the system has reached a final stable state suitable for packaging. Here, the second turbidity threshold is a preset, more stringent upper limit for turbidity fluctuation range than the first turbidity threshold, for example, it can be set to 2 NTU, used to determine that the top clear liquid layer is extremely uniform, without any microscopic aggregates or flocculation invisible to the naked eye; the drift threshold is a preset upper limit for the percentage change in conductivity, for example, it can be set to 0.5%, used to determine that the ion distribution is highly uniform, with no concentration gradient; the temperature uniformity threshold is a preset maximum allowable temperature difference within the tank, for example, it can be set to 0.5℃, used to determine that there is no significant risk of thermal convection disturbance within the system. The effect of this step is to ensure that the product is not only macroscopically clear, but also achieves high uniformity and thermodynamic stability in its microstructure and physicochemical properties, fundamentally preventing the risk of performance degradation during storage.

[0085] If the cumulative time since entering the initial clarification state exceeds the preset maximum stability assessment time t. w If any of the above stability conditions are still not met, the system will automatically initiate a control program. This program includes starting the circulation pump at a speed 30-50% lower than the rated speed during stirring to perform gentle recirculation, and regulating and maintaining the system temperature within ±1°C of the process reference temperature through the settling tank jacket. The maximum stability assessment time t is specified here. wThis is a preset time limit, such as 48 hours, to avoid indefinite production delays caused by waiting for the system to stabilize naturally. The process reference temperature is a preset target temperature value most suitable for the system's stability, such as 35°C. Its purpose is to eliminate local concentration or temperature gradients through gentle mechanical mixing and to promote structural reorganization of incompletely stable associative compounds using thermal equilibrium until the system once again meets all stability conditions. This closed-loop control mechanism significantly improves the tolerance of the sedimentation process and the batch yield of the final product, ensuring that even with minor fluctuations in raw materials or the environment, high-stability products with consistent performance can be produced through process adjustments.

[0086] In another embodiment, the preparation method of the ultra-micro associative emulsion modifier includes the following specific steps in step 3): collecting a first finished product sample through a first automatic sampling valve installed on the discharge pipeline of the settling tank, and collecting a second finished product sample through a second automatic sampling valve installed before the inlet of the packaging unit; transporting the first and second finished product samples to the same or multiple analytical instruments for parallel testing; when the test results of the first and second finished product samples are consistent and both meet the preset qualification standards, the control system automatically authorizes the packaging unit to complete the packaging and warehousing of the current batch of products; when the test results of the first and second finished product samples are inconsistent, or any test result does not meet the preset qualification standards, the control system automatically locks the packaging unit and triggers an audible and visual alarm, while guiding the current batch of materials to an isolation storage tank.

[0087] To address the problems associated with relying on single-time-point and single-location sampling in the final product testing of modulators—namely, the difficulty in ensuring the overall homogeneity of materials within large-volume tanks, the inability to identify localized quality defects, and the potential for delayed manual testing decisions leading to the erroneous release of defective products or the misjudgment of qualified products—this solution provides an online quality judgment and process control system based on dual-point automatic sampling and real-time parallel testing. This solution installs a first automatic sampling valve on the settling tank outlet pipeline to collect the first finished product sample, and a second automatic sampling valve on the conveying pipeline before the packaging unit inlet to collect the second finished product sample. The purpose of this dual-point sampling is to obtain samples from two key spatial nodes: the product flowing out of the storage unit and entering the final packaging unit. This cross-validates the homogeneity and stability of the material throughout the entire output stage from the tank to the packaging line, effectively overcoming sampling errors caused by slight concentration gradients or stratification that may exist within the storage tank.

[0088] Transporting the first finished product sample and the second finished product sample to the analytical instrument for parallel detection respectively is the core step to achieve efficient and accurate quality judgment. The purpose of parallel detection is to immediately analyze the key performance indicators of two independently sourced samples simultaneously, such as measuring the interfacial tension, turbidity, and conductivity. By comparing the detection data of the two samples at the same moment, the system can immediately identify whether there is a significant difference beyond the process tolerance range between the two. The preset passing criteria relied on by this step are the unified basis for judging whether the product quality meets the standard. For example, the interfacial tension needs to be between 1.0×10 - 2 mN / m and 3.0×10 -2 mN / m, and the turbidity needs to be lower than 5 NTU. These specific numerical ranges are the preset passing criteria, which define the quantitative thresholds that the product must meet to be qualified.

[0089] When the detection results of the first finished product sample and the second finished product sample are consistent and both meet the preset passing criteria, the control system automatically authorizes the packaging unit to complete the packaging and warehousing of the current batch of products. The effect of this step is to achieve seamless automated linkage between quality verification and downstream production operations. Only products that have passed double independent verifications and are confirmed to meet the standards can be released, thus fundamentally ensuring the quality reliability and batch consistency of the products leaving the factory. If the detection results of the first finished product sample and the second finished product sample are inconsistent, or any detection result does not meet the preset passing criteria, the control system automatically locks the packaging unit and triggers an audible and visual alarm, while guiding the current batch of materials to the isolation storage tank. Here, the detection result inconsistency means that the measured value difference of the two independent samples in the same key performance indicator exceeds the preset allowable deviation range. For example, the difference in interfacial tension between the two samples is greater than 0.5×10 -2 mN / m. The purpose of this step is to establish a rapid-response quality and safety interception and isolation mechanism. Once signs of uneven quality or single-point nonconformity are detected, the system can immediately interrupt the production process, prevent potential nonconforming products from entering the packaging link, and physically isolate the problem materials for further manual verification and disposal, thereby forming a complete and automated production quality and safety closed-loop.

[0090] In another solution, in the preparation method of the ultra-fine associative emulsion displacement agent, when preparing a displacement agent containing polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate, step S1.7 specifically includes the following steps: S1.7.1. Divide the balance water to be added into the fourth part of water and the fifth part of water, where the fourth part of water accounts for 30%-50% of the total amount of the balance water; S1.7.2. Use the water from the fourth part to mix with the formulated amounts of polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano titanium dioxide and sodium citrate, and disperse using a high-speed disperser at 1500-3000 rpm for 15-30 min to form a composite synergistic dispersion. S1.7.3 Under the condition of maintaining stirring, add the composite synergistic dispersion obtained in step S1.7.2 to the mixture obtained in step S1.6; S1.7.4 Add water from the fifth part to bring the total water volume and total concentration of the system to the level specified in the formula.

[0091] To address the technical challenge of introducing synergistic components such as polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate into a basic formulation system, where the significant differences in their physicochemical properties can easily lead to uneven dispersion, aggregation, or gelation if conventional mixing methods are used, thus severely impacting the interfacial activity, stability, and synergistic effect of the final product, this solution provides a fine dispersion and integration process specifically designed for this composite system. This process aims to ensure that each synergistic component is fully dissolved, dispersed, and uniformly integrated into the formed ultra-micro-associated emulsion matrix, thereby maximizing their synergistic effect.

[0092] The process first divides the equilibrium water to be added into a fourth and a fifth portion, with the fourth portion comprising 30%-50% of the total equilibrium water. The purpose of this step is to allocate a specific volume of water for the pretreatment of the synergistic components, ensuring sufficient medium for subsequent dispersion operations and maintaining accurate final total concentration. Its effect is to create independent, appropriately concentrated operating conditions for the pre-dispersion of key synergistic components.

[0093] Subsequently, the fourth component (water) was mixed with the formulated amounts of polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate, and dispersed using a high-speed disperser at 1500-3000 rpm for 15-30 minutes to form a composite synergistic dispersion. The high-speed disperser used here is a mixing device capable of generating high shear forces. Its preset speed range and dispersion time are designed to provide sufficient mechanical energy to ensure complete dissolution of the hydrophilic polymer hydroxypropyl methylcellulose, thorough deagglomeration and stable suspension of the nano-titanium dioxide particles, and uniform distribution of the polyglycerol ester and sodium citrate. The effect is that these synergistic components are pre-treated into a highly homogeneous and stable dispersion system with full interaction between the components, avoiding potential problems of excessively high local concentrations or poor dispersion when directly added to the main system.

[0094] While maintaining stirring of the main system, the prepared composite synergistic dispersion is added to the main mixture that has been assembled from polyether-modified polysiloxane and anionic surfactant. The purpose of this step is to smoothly introduce the synergistic system into the main associated structure system under dynamic mixing conditions, utilizing gentle shear forces to promote the gradual fusion of the two. The effect is to achieve effective bonding between the functional enhancing component and the core surfactant associative complex, which helps the synergistic component to be positioned at the interface or in the aqueous network to perform its intended function.

[0095] Finally, water is added to bring the total water volume and concentration of the entire system to the level specified in the formulation. The purpose of this step is to calibrate and homogenize the final system concentration, ensuring that the product meets stringent specifications. The ultimate result is a highly dispersed, synergistically integrated, and stable ultra-micro-associated emulsion modifier.

[0096] Example 4 Based on the step-by-step assembly process of Example 2, additional synergistic components were added: 0.008t of polyglycerol-6 didecanoate, 0.003t of hydroxypropyl methylcellulose, 0.0008t of nano-titanium dioxide, and 0.002t of sodium citrate. The basic formulation ingredients were the same as in Example 2: 0.614t of water, 0.203t of polyether-modified polysiloxane, 0.170t of sodium α-olefin sulfonate, and 0.013t of sodium dodecyl sulfate. First, the basic associative emulsion was prepared entirely according to the steps of Example 2 (i.e., step S1.6 was completed). Then, the equilibrium water to be added (approximately 25% of the total water volume) was divided into two parts: 40% of it was taken as the fourth part of water and mixed with all the synergistic components. The mixture was dispersed at 2200 rpm for 20 min using a high-speed disperser to form a homogeneous synergistic dispersion. While maintaining the stirring of the basic associative emulsion, this composite synergistic dispersion was slowly added to it, and finally the remaining fifth part of water was added to balance to the total concentration. The mixture was allowed to settle for 24 hours to obtain the final product. The performance comparison results between Example 4 (stepwise sequential assembly method, including synergistic components) and Example 2 (stepwise sequential assembly method, basic formulation) are shown in Table 5.

[0097] Table 5 Performance Comparison Results of Example 4 and Example 2

[0098]

[0099] In summary, compared to Example 2 (stepwise sequential assembly method), which already demonstrated excellent performance, Example 4, while employing the same stepwise assembly process, achieved significant improvements in all core performance indicators, including wash-off efficiency, interfacial activity, wetting modification ability, microstructure uniformity, temperature resistance, salt resistance, and long-term stability, by introducing synergistic components such as polyglycerol-6 didecanoate and combining them with a dedicated high-speed dispersion pretreatment and integration process. This indicates that, under the premise of obtaining a highly ordered and structurally stable basic associative body through the stepwise sequential assembly process, the synergistic components and their dedicated dispersion and integration process can be effectively coupled with it. Through multiple synergistic mechanisms such as reinforcing the interfacial film, constructing an aqueous network, modifying the rock surface, and creating a balanced ion environment, the comprehensive performance of the modulator is elevated to a new level. Example 4 confirms that this scheme can effectively solve the problem of uniform dispersion and stable integration of multifunctional synergistic components in complex ultramicro-associated systems, providing a reliable technical path for developing high-performance modulators suitable for extreme reservoir conditions.

[0100] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A micro-associated emulsion modifier, characterized in that, The components include the following parts by weight: Water 0.40-0.70 parts, polyether-modified polysiloxane 0.15-0.25 parts, sodium α-olefin sulfonate 0.12-0.20 parts and sodium dodecyl sulfate 0.005-0.020 parts.

2. The ultrafine associative emulsion modifier as described in claim 1, characterized in that, It also includes the following components in parts by weight: 0.10-0.20 parts of ethylene glycol.

3. The ultrafine associative emulsion modifier as described in claim 1, characterized in that, It also includes the following components in parts by weight: Polyglycerol-6 didecanoate 0.005-0.020 parts, hydroxypropyl methylcellulose 0.001-0.008 parts, nano titanium dioxide 0.0005-0.003 parts, sodium citrate 0.001-0.005 parts.

4. A method for preparing an ultrafine associative emulsion modifier as described in any one of claims 1-3, characterized in that, Includes the following steps: 1) Add water to the mixing tank, and add the other raw material components to the mixing tank, stirring to dissolve; 2) After the material is thoroughly mixed, allow it to settle; 3) Sampling and testing are conducted, and the samples are packaged and stored after passing the tests.

5. The preparation method of the ultrafine associative emulsion modifier as described in claim 4, characterized in that, Step 1) specifically includes the following steps: S1.

1. Mix the first portion of water, which accounts for 10%-20% of the total water volume, with sodium chloride to prepare a sodium chloride solution with a mass concentration of 0.5%-2.0%. S1.2 Add sodium α-olefin sulfonate to the sodium chloride solution prepared in step S1.1, stir until completely dissolved, and let it stand at 25-40℃ for 0.5-2 hours to form an ion-controlled premixed solution; S1.

3. Use the second portion of water, which accounts for 15%-25% of the total water volume, to dissolve the polyether-modified polysiloxane separately to form a polyether-modified polysiloxane premix. S1.

4. Use the third portion of water, which accounts for 10%-20% of the total water volume, to dissolve sodium dodecyl sulfate separately to form a sodium dodecyl sulfate premixed solution; S1.5 Under stirring conditions, the sodium dodecyl sulfate premix obtained in step S1.4 is first added to the ion-regulating premix obtained in step S1.2 and mixed evenly to form an anionic composite premix. S1.

6. While maintaining stirring, slowly and evenly add the polyether-modified polysiloxane premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes. S1.7 Finally, add the remaining equilibrium water to bring the system to the total water volume and total concentration specified in the formula.

6. The preparation method of the ultrafine associative emulsion modifier as described in claim 5, characterized in that, When preparing a retarder containing ethylene glycol, step S1.3 specifically involves: Use a second portion of water, which accounts for 15%-25% of the total water volume, to dissolve the polyether-modified polysiloxane and ethylene glycol together to form a siloxane-ethylene glycol premix. Step S1.6 specifically includes: While maintaining stirring, slowly and evenly add the siloxane-ethylene glycol premix obtained in step S1.3 to the anionic composite premix obtained in step S1.5 within 30-60 minutes.

7. The preparation method of the ultrafine associative emulsion modifier as described in claim 4, characterized in that, Between step 1) and step 2), there is also an online monitoring and intelligent control step: S1. Real-time acquisition of solution temperature T, conductivity K, and instantaneous power P of the stirring motor in the mixing system; and periodic sampling to measure the dynamic interfacial tension value γ of the mixing system; S2. Calculate the three process control indicators: Temperature deviation ΔT = T – T t T t The preset process reference temperature; the rate of change of electrical conductivity K' = dK / dt; the cumulative stirring work E = ∫P(t)dt, with the integration interval from the stirring start time t0 in step 1) to the current time t; S3. Set and judge the following three conditions: Condition 1: Rate of change of conductivity K' ≤ K' th ;where K' th The threshold value for the rate of change of conductivity is a preset value used to determine that the dissolution and ion pre-assembly processes have become relatively stable. Condition 2: The dynamic interfacial tension value γ satisfies γ min ≤ γ ≤ γ max ;wherein γ min With γ max These are the lower and upper limits of the preset dynamic interfacial tension acceptable range, which are used to determine whether the system has reached the target interfacial activity. Condition 3: Cumulative stirring work E ≥ E th ; where E th This is a preset threshold for the cumulative stirring work used to determine whether the mixing system has obtained sufficient stirring energy; S4. When conditions 1, 2 and 3 are simultaneously met for the first time during the monitoring process, the dissolution and pre-assembly are determined to be complete, and then the process proceeds to step 2) for sedimentation. S5. If, starting from the stirring start time t0 in step 1), conditions 1, 2, and 3 are not simultaneously satisfied when the initial set time T1 is reached, then the following corresponding control operations will be performed based on the unsatisfied combination of conditions: S5.1 If condition one is not met, but conditions two and three are both met, then increase the stirring rate to 110%-130% of the current rate and set the first additional monitoring duration △t1. S5.2 If condition two is not satisfied, but conditions one and three are satisfied, then set a second additional stirring time Δt2, where Δt2 is 10-30 min; S5.3 If neither condition one nor condition two is satisfied, but condition three is satisfied, then perform the following operations in sequence: first increase the stirring rate to 110%-130% of the current rate, and then immediately set the second additional stirring time △t2. S5.4 If condition three is not met, but conditions one and two are met, and ΔT > 2℃, then the constant temperature control system is activated to adjust and maintain the temperature of the mixture at T. t Within the range of ± 1℃, and set the first additional monitoring duration △t1; S5.5 If condition three is not satisfied, but conditions one and two are satisfied, and ΔT ≤ 2℃, then increase the stirring rate to 110%-130% of the current rate, and set a third additional stirring time Δt3, where Δt3 is 10-30 min; S5.6 If neither condition 1 nor condition 3 is satisfied, but condition 2 is satisfied, then execute S5.1 first. After the first additional monitoring duration △t1 ends, if △T > 2℃, then execute S5.4; if △T ≤ 2℃, then execute S5.

5. S5.7 If conditions two and three are not met, but condition one is met, then execute S5.2 first. After the second additional stirring time Δt2 ends, if ΔT > 2℃, then execute S5.4; if ΔT ≤ 2℃, then execute S5.

5. S5.8 If conditions 1, 2, and 3 are not met, then proceed with S5.3 in sequence. After the second additional stirring time Δt2 ends, if ΔT > 2℃, proceed with S5.4; if ΔT ≤ 2℃, proceed with S5.

5. S6. After executing any of the control operations in S5, continue monitoring and judgment within the corresponding additional time period; If conditions one, two, and three are simultaneously satisfied before the end of any additional time period, the dissolution and pre-assembly are deemed successful, and the process proceeds to step 2). If, starting from the stirring start time t0 in step 1), the accumulated time reaches the preset maximum total processing time T... max If conditions one, two, and three are still not met simultaneously, the batch is determined to be an abnormally mixed batch. Stirring is immediately stopped, the material in the current preparation tank is locked, and an audible and visual alarm is triggered, awaiting manual intervention.

8. The preparation method of the ultrafine associative emulsion modifier as described in claim 4, characterized in that, Step 2) of the settlement process specifically includes the following steps: S3.1 Real-time monitoring of the turbidity values ​​at least three preset height levels from top to bottom inside the settling tank, and simultaneous monitoring of the real-time turbidity and conductivity values ​​in the discharge pipeline at the bottom of the settling tank. S3.2 When the rate of change of real-time turbidity values ​​at all preset height levels is simultaneously lower than the first rate of change threshold, and the real-time turbidity value in the discharge pipeline at the bottom of the settling tank is lower than the first turbidity threshold, the system is determined to have reached the primary clarification state. S3.

3. Upon reaching the initial clarification state, the stability assessment phase begins, during which the following monitoring is performed simultaneously: S3.3.1 Monitor the turbidity fluctuation range of the clear liquid layer at the top of the settling tank; the turbidity fluctuation range is obtained by recording the highest and lowest turbidity readings within a continuous monitoring cycle in this stage and calculating the difference between the two. S3.3.2 Monitor the real-time conductivity value in the discharge pipeline at the bottom of the settling tank and calculate its drift degree; the drift degree is the absolute percentage change of the real-time conductivity value relative to the initial conductivity value in this stage; S3.3.3 , By installing at least two temperature probes at different heights inside the settling tank, monitor and calculate the maximum temperature difference inside the settling tank; S3.

4. When all of the following conditions are met simultaneously and maintained for a preset stabilization period, the settlement is deemed complete and the system reaches its final stable state: Condition A: The turbidity fluctuation of the clear liquid layer at the top of the settling tank is lower than the second turbidity threshold, and the second turbidity threshold is lower than the first turbidity threshold; Condition B: The drift of the real-time conductivity value in the discharge pipeline at the bottom of the settling tank is lower than the preset drift threshold; Condition C: The maximum temperature difference inside the settling tank is lower than the preset temperature uniformity threshold; S3.5 If the cumulative time since entering the initial clarification state exceeds the preset maximum stability assessment time t w If at least one of conditions A, B, and C is not met, the control procedure will be automatically initiated. The control procedure includes: starting the circulation pump to recirculate the material in the tank at a speed 30%-50% lower than the rated speed during the stirring operation in step 1), while simultaneously adjusting and maintaining the system temperature within the range of ±1℃ of the process reference temperature through the settling tank jacket; the control procedure will continue to be executed until conditions A, B, and C are simultaneously satisfied and the preset maximum stability assessment time t is maintained. w .

9. The preparation method of the ultrafine associative emulsion modifier as described in claim 4, characterized in that, Step 3) includes the following specific steps: A first finished product sample is collected by a first automatic sampling valve installed on the discharge pipeline of the settling tank, and a second finished product sample is collected by a second automatic sampling valve installed before the inlet of the packaging unit. The first and second finished product samples are respectively sent to the same or multiple analytical instruments for parallel testing; When the test results of the first finished product sample and the second finished product sample are consistent and both meet the preset qualification standards, the control system automatically authorizes the packaging unit to complete the packaging and warehousing of the current batch of products. When the test results of the first finished product sample and the second finished product sample are inconsistent, or when any test result does not meet the preset qualification standard, the control system automatically locks the packaging unit and triggers an audible and visual alarm, while guiding the current batch of materials to an isolation storage tank.

10. The preparation method of the ultrafine associative emulsion modifier as described in claim 5, characterized in that, When preparing a retarder comprising polyglycerol-6-didecanoate, hydroxypropyl methylcellulose, nano-titanium dioxide, and sodium citrate, step S1.7 specifically includes the following steps: S1.7.1 Divide the balance water to be added into a fourth part and a fifth part, wherein the fourth part accounts for 30%-50% of the total balance water; S1.7.

2. Use water from the fourth part, mix it with polyglycerol-6 didecanoate, hydroxypropyl methylcellulose, nano titanium dioxide and sodium citrate, and disperse it at 1500-3000 rpm for 15-30 min using a high-speed disperser to form a composite synergistic dispersion. S1.7.3 Under the condition of maintaining stirring, add the composite synergistic dispersion obtained in step S1.7.2 to the mixture obtained in step S1.6; S1.7.4 Add water from the fifth part to bring the total water volume and total concentration of the system to the level specified in the formula.

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