Cleaning compositions with organic acid synergistic complex nanoadsorbents and methods of making same

Abstract

The present application relates to the technical field of environment-friendly cleaning agent, and discloses a cleaning composition of organic acid synergistic composite nano adsorbent and a preparation method thereof, which comprises the following components in percentage by mass: 1-3% of sulfamic acid; 5-10% of citric acid; 2-5% of sodium gluconate; 5-20% of alkyl polyglycoside; 0.1-1.5% of composite functional nano adsorbent; 1-4% of pH regulator; and the balance of deionized water. The present application creates a new path of physical solidification for active removal, and through the action of the composite functional nano adsorbent, Ca + , Mg + and other metal ions released by pollutants during the cleaning process are instantaneously solidified by the nano surface complexing agent through coordination; at the same time, organic pollutants such as oil and fat are efficiently captured by the hydrophobic capture aid through hydrophobic interaction. This makes most of the pollutants firmly fixed in the interior or on the surface of the adsorbent solid particles during the cleaning stage.

Description

Technical Field

[0001] This invention relates to the field of environmentally friendly cleaning agents, specifically to a cleaning composition and preparation method of an organic acid synergistic composite nano-adsorbent. Background Technology

[0002] The glass surface of photovoltaic modules easily accumulates dust, pollen, and other particulate matter, forming biofilms. Especially in hard water areas, cleaning with water containing calcium and magnesium ions leaves behind scale and mineral deposits after water evaporation. These opaque deposits significantly obstruct light transmission, directly reducing the power generation efficiency of photovoltaic modules and accelerating module aging due to the "hot spot effect," thus shortening their lifespan.

[0003] High-rise glass curtain walls and high-performance coatings must withstand a variety of complex pollutants, including acid rain corrosion, bird droppings, industrial fumes, and vehicle exhaust. These contaminants are complex in composition, containing both inorganic salts and organic oils. The cleaning process not only requires efficient removal of these stubborn stains, but more importantly, it must ensure that the cleaning agent does not corrode, scratch, or leave low residue on the glass, metal frame, and special coatings (such as anti-reflective coatings and self-cleaning coatings) to maintain their aesthetic appearance and functionality.

[0004] To address the aforementioned issues, current mainstream cleaning agents primarily rely on a compound system of acidic descaling agents (sulfamic acid, citric acid, etc.) and polymeric dispersants (sodium polyaspartate). Although chemical dispersion technology, represented by sodium polyaspartate, has achieved some success in inhibiting scale, its technical approach suffers from three inherent drawbacks that severely restrict its further application and development in high-value, large-area cleaning scenarios:

[0005] (1) Secondary pollution is a serious problem, and subsequent treatment costs are high.

[0006] The core mechanism of action of sodium polyaspartate is to remove pollutants (such as Ca²⁺) + Mg² + Instead of completely removing pollutants from the system, the wastewater undergoes "physical encapsulation" and "state transfer." This results in high concentrations of contaminants in the post-cleaning wastewater, present as soluble complexes or fine suspended particles. Direct discharge of such wastewater, rich in chemicals and inorganic salts, will pollute the environment. Therefore, users or professional cleaning companies must perform complex secondary chemical treatments on the wastewater, such as adding coagulants and flocculants for sedimentation and adjusting the pH to neutral, to meet environmental discharge standards. This process is not only cumbersome but also costly.

[0007] (2) The core additives are expensive and highly dependent on raw materials.

[0008] Sodium polyaspartate, a high-value-added fine chemical synthesized through chemical synthesis, has a production cost far exceeding that of traditional inorganic phosphate additives. This results in persistently high overall formulation costs, posing a significant economic burden for scenarios requiring large-scale application, such as photovoltaic power plant operations. Furthermore, existing technologies largely rely on single-type dispersants like sodium polyaspartate, which cannot effectively address complex fouling with varying compositions.

[0009] (3) Insufficient capacity for synergistic treatment of complex fouling

[0010] Sodium polyaspartate's dispersing effect is primarily targeted at inorganic ions, and its molecular structure has a weak affinity for non-polar organic contaminants. In actual cleaning processes, sodium polyaspartate cannot effectively capture and fix contaminants such as grease, organic residues, and biological debris that detach from the surface. These organic contaminants may flow with the waste liquid, causing cross-contamination, or they may re-adhere to the cleaned surface during solution evaporation due to loss of dispersion protection, forming "hidden dirt" and affecting the durability of the cleaning effect.

[0011] In summary, existing cleaning technologies based on polymer dispersants have inherent drawbacks, such as their inability to fundamentally remove contaminants, the existence of secondary pollution, high costs, and limited ability to handle complex dirt, making it difficult to meet the growing demand for efficient, environmentally friendly, and low-cost surface cleaning and maintenance in fields such as photovoltaics and high-end buildings. Summary of the Invention

[0012] The purpose of this invention is to address the shortcomings of existing technologies by providing a cleaning composition of organic acid synergistic composite nano-adsorbent and its preparation method, which has the ability to simultaneously and efficiently solidify inorganic and organic pollutants, and can be used for cleaning photovoltaic modules, high-altitude glass curtain walls and special coating surfaces.

[0013] To achieve this objective, the present invention adopts the following technical solution:

[0014] On one hand, the present invention provides a cleaning composition of an organic acid synergistic composite nano-adsorbent, comprising the following components by mass percentage:

[0015] 1%-3% aminosulfonic acid;

[0016] Citric acid 5%-10%;

[0017] Sodium gluconate 2%-5%;

[0018] Alkyl glycosides 5%-20%;

[0019] Composite functional nano-adsorbents: 0.1%-1.5%;

[0020] pH adjuster 1%-4%;

[0021] Deionized water balance.

[0022] As a preferred embodiment of the organic acid synergistic composite nano-adsorbent, it comprises the following components by mass percentage:

[0023] 2% aminosulfonic acid;

[0024] Citric acid 10%;

[0025] 3% sodium gluconate;

[0026] Alkyl glycosides 12%;

[0027] Composite functional nano-adsorbent 1%;

[0028] pH adjuster 3%;

[0029] Deionized water balance.

[0030] As a preferred embodiment of the organic acid synergistic composite nano-adsorbent, the composite functional nano-adsorbent comprises the following components by mass percentage:

[0031] Nano-surface complexing agent 50%-80%;

[0032] Hydrophobic trapping agent 20%-50%.

[0033] As a preferred embodiment of organic acid synergistic composite nano-adsorbent, the nano-surface complexing agent is one or more of titanium dioxide and zinc oxide nanoparticles.

[0034] As a preferred embodiment of organic acid synergistic composite nano-adsorbent, the hydrophobic trapping agent is one or more of modified polydimethylsiloxane and polymethylsilsesquioxane.

[0035] As a preferred embodiment of the organic acid synergistic composite nano-adsorbent, the modified polydimethylsiloxane is prepared as follows:

[0036] H-PDMS prepolymer with an average molecular weight of (10000±5000) g / mol and allyl-terminated polyether with an average molecular weight of (3500±1000) g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, and an appropriate amount of toluene was added as a solvent. The system was heated to 110°C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0037] As a preferred embodiment of the organic acid synergistic composite nano-adsorbent, the pH adjuster is one or more of sodium hydroxide and potassium hydroxide.

[0038] On the other hand, the present invention provides a method for preparing a cleaning composition of the above-mentioned organic acid synergistic composite nano-adsorbent, comprising the following steps:

[0039] S1. Preparation of composite functional nano-adsorbents;

[0040] S2. While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0041] S3. Add the alkyl glycoside to the solution and stir until homogeneous;

[0042] S4. Slowly add the composite functional nano-adsorbent into the solution and use a high-shear or ultrasonic dispersion device to fully disperse it so that the adsorbent particles are uniformly and stably suspended in the solution.

[0043] S5. Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0~4.0 to obtain a clean composition.

[0044] A preferred embodiment of the method for preparing a cleaning composition of an organic acid synergistic composite nano-adsorbent includes step S1 specifically comprising:

[0045] S11. Place the nano-surface complexing agent and the hydrophobic trapping agent in a vacuum drying oven at 80℃ and dry for 4-6 hours.

[0046] S12. Place the dried nano-surface complexing agent and hydrophobic trapping agent into a high-speed mixer and stir and mix at a speed of 500-1000 rpm for 15 minutes.

[0047] S13. Transfer the premixed powder from step S12 to a high-energy ball mill for high-energy ball milling. The ball milling time is 1-3 hours and the rotation speed is 300-600 rpm.

[0048] S14. The powder after compounding in step S13 is sieved through a standard sieve of 100-150 mesh to remove agglomerates or large particles, thereby obtaining a composite functional nano-adsorbent.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) This invention completely overturns the passive approach of traditional chemical dispersion and pioneers a new active removal pathway through physical solidification. Through the action of composite functional nano-adsorbents, the Ca²⁺ released by pollutants during the cleaning process is effectively removed. + Mg² +Metal ions are instantly solidified by nano-surface complexing agents through coordination; simultaneously, organic pollutants such as grease are efficiently captured by hydrophobic trapping agents through hydrophobic interactions. This ensures that the vast majority of pollutants are firmly fixed inside or on the surface of the adsorbent solid particles during the cleaning stage. Therefore, the content of dissolved and suspended pollutants in the wastewater generated after cleaning is extremely low, eliminating the need for complex secondary chemical treatment processes such as coagulation, sedimentation, and neutralization, thus meeting or even far exceeding environmental emission requirements. This greatly simplifies the post-treatment process and significantly reduces overall cleaning costs and environmental pressure.

[0051] (2) The core of this invention lies in the synergistic design of composite functional nano-adsorbents. The abundant active hydroxyl groups on the surface of the nano-surface complexing agent can efficiently complex metal ions such as calcium and magnesium, which is dedicated to solving the problem of inorganic scale. Meanwhile, the hydrophobic capture aid specifically captures non-polar organic pollutants such as grease and oil film. This synergistic mechanism of "inorganic-organic dual targeting" enables the composition to simultaneously and efficiently remove the complex mixed dirt commonly found on the surface of photovoltaic modules and glass curtain walls, solving the bottleneck problem of the weak ability of traditional single dispersants to treat organic pollutants and improving the cleaning effect.

[0052] (3) This invention eliminates secondary deposition at the source. Because pollutants are solidified by the adsorbent and stably exist in the cleaning solution the moment they are generated or stripped, this technology eliminates Ca²⁺ at its source. + Mg² + This eliminates the risk of plasma re-precipitating and forming water stains or secondary mineral scale on the clean surface. Simultaneously, it effectively prevents the re-adhesion of detached organic contaminants due to loss of dispersion protection. This not only ensures high surface cleanliness and high light transmittance after a single cleaning but also avoids potential damage to photovoltaic module glass covers, curtain wall glass, and special coatings caused by repeated contamination and cleaning, thus helping to extend service life.

[0053] (4) The nano-surface complexing agent and hydrophobic trapping agent used in this invention are materials that have been mass-produced. Their raw materials are widely available and their costs are controllable. Compared with fine chemicals such as sodium polyaspartate, which have complex synthesis processes and high prices, they have a greater cost advantage. Detailed Implementation

[0054] To better illustrate the objectives, technical solutions, and advantages of this invention, the following embodiments are provided. Obviously, the following embodiments are only a part of the embodiments of this invention, and not all of them; it should be understood that the embodiments of this invention are only used to illustrate the technical effects of this invention, and not to limit the scope of protection of this invention.

[0055] All raw materials used in the examples are commercially available; unless otherwise specified, the reagents, methods and equipment used in this invention are conventional reagents, methods and equipment in this technical field.

[0056] Example 1:

[0057] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0058] 2% aminosulfonic acid;

[0059] Citric acid 10%;

[0060] 3% sodium gluconate;

[0061] Alkyl glycosides 12%;

[0062] Composite functional nano-adsorbent 0.5%;

[0063] pH adjuster 3%;

[0064] Deionized water balance;

[0065] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0066] (1) Preparation of composite functional nano-adsorbent (50% TiO2 + 50% modified PDMS):

[0067] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0068] By mass percentage, 50% of titanium dioxide and 50% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0069] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0070] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0071] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0072] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0073] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0074] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0075] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0076] Example 2:

[0077] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0078] 2% aminosulfonic acid;

[0079] Citric acid 10%;

[0080] 3% sodium gluconate;

[0081] Alkyl glycosides 12%;

[0082] Composite functional nano-adsorbent 0.5%;

[0083] pH adjuster 3%;

[0084] Deionized water balance;

[0085] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0086] (1) Preparation of composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS):

[0087] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0088] By mass percentage, 60% of titanium dioxide and 40% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0089] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0090] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0091] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0092] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0093] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0094] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0095] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0096] Example 3:

[0097] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0098] 2% aminosulfonic acid;

[0099] Citric acid 10%;

[0100] 3% sodium gluconate;

[0101] Alkyl glycosides 12%;

[0102] Composite functional nano-adsorbent 0.8%;

[0103] pH adjuster 3%;

[0104] Deionized water balance;

[0105] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0106] (1) Preparation of composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS):

[0107] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0108] By mass percentage, 60% of titanium dioxide and 40% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0109] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0110] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0111] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0112] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0113] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0114] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0115] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0116] Example 4:

[0117] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0118] 2% aminosulfonic acid;

[0119] Citric acid 10%;

[0120] 3% sodium gluconate;

[0121] Alkyl glycosides 12%;

[0122] Composite functional nano-adsorbent 1.0%;

[0123] pH adjuster 3%;

[0124] Deionized water balance;

[0125] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0126] (1) Preparation of composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS):

[0127] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0128] By mass percentage, 60% of titanium dioxide and 40% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0129] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0130] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0131] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0132] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0133] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0134] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0135] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0136] Example 5:

[0137] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0138] 2% aminosulfonic acid;

[0139] Citric acid 10%;

[0140] 3% sodium gluconate;

[0141] Alkyl glycosides 12%;

[0142] Composite functional nano-adsorbent 1.2%;

[0143] pH adjuster 3%;

[0144] Deionized water balance;

[0145] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0146] (1) Preparation of composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS):

[0147] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0148] By mass percentage, 60% of titanium dioxide and 40% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0149] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0150] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0151] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0152] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0153] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0154] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0155] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0156] Example 6:

[0157] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0158] 2% aminosulfonic acid;

[0159] Citric acid 10%;

[0160] 3% sodium gluconate;

[0161] Alkyl glycosides 12%;

[0162] Composite functional nano-adsorbent 1.5%;

[0163] pH adjuster 3%;

[0164] Deionized water balance;

[0165] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0166] (1) Preparation of composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS):

[0167] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0168] By mass percentage, 60% of titanium dioxide and 40% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0169] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0170] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0171] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0172] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0173] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0174] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0175] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0176] Example 7:

[0177] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0178] 2% aminosulfonic acid;

[0179] Citric acid 10%;

[0180] 3% sodium gluconate;

[0181] Alkyl glycosides 12%;

[0182] Composite functional nano-adsorbent 0.5%;

[0183] pH adjuster 3%;

[0184] Deionized water balance;

[0185] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0186] (1) Preparation of composite functional nano-adsorbent (70% TiO2 + 30% modified PDMS):

[0187] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0188] By mass percentage, 70% of titanium dioxide and 30% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0189] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0190] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0191] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0192] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0193] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0194] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0195] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0196] Example 8:

[0197] The cleaning composition of the organic acid synergistic composite nano-adsorbent in this embodiment is obtained by reacting the following raw materials in mass percentage:

[0198] 2% aminosulfonic acid;

[0199] Citric acid 10%;

[0200] 3% sodium gluconate;

[0201] Alkyl glycosides 12%;

[0202] Composite functional nano-adsorbent 0.5%;

[0203] pH adjuster 3%;

[0204] Deionized water balance;

[0205] When preparing a cleaning composition for an organic acid synergistic composite nano-adsorbent, each raw material is added in the amounts described above, including the following steps:

[0206] (1) Preparation of composite functional nano-adsorbent (80% TiO2 + 20% modified PDMS):

[0207] H-PDMS prepolymer with an average molecular weight of 10000 g / mol and allyl-terminated polyether with an average molecular weight of 3500 g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, with an appropriate amount of toluene added as a solvent. The system was heated to 110 °C and kept stable under an inert gas atmosphere (such as nitrogen). Platinum catalyst was slowly added dropwise, and after the addition was complete, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane.

[0208] By mass percentage, 80% of titanium dioxide and 20% of modified polydimethylsiloxane were placed in a vacuum drying oven at 80°C and dried for 4 hours.

[0209] The dried titanium dioxide and modified polydimethylsiloxane were placed in a high-speed mixer and stirred at 500 rpm for 15 minutes.

[0210] The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 3 hours at a speed of 300 rpm.

[0211] The above-mentioned composite powder was sieved through a 100-mesh standard sieve to remove agglomerates or large particles, thus obtaining a composite functional nano-adsorbent.

[0212] (2) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0213] (3) Add the alkyl glycoside to the solution and stir until homogeneous;

[0214] (4) The composite functional nano-adsorbent is slowly added to the solution and fully dispersed using a high-shear or ultrasonic dispersion device so that the adsorbent particles are uniformly and stably suspended in the solution.

[0215] (5) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0 to obtain a clean composition.

[0216] Comparative Example 1 (Traditional Dispersant System):

[0217] The cleaning agent in this comparative example, a conventional dispersant system, is obtained by reacting the following raw materials in a mass percentage:

[0218] 2% aminosulfonic acid;

[0219] Citric acid 10%;

[0220] 3% sodium gluconate;

[0221] Alkyl glycosides 12%;

[0222] Sodium polyaspartate 0.5%;

[0223] pH adjuster 3%;

[0224] Deionized water balance;

[0225] When preparing a cleaning agent based on a traditional dispersant system, the raw materials are added according to the above-mentioned amounts, including the following steps:

[0226] (1) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0227] (2) Add the alkyl glycoside to the solution and stir until homogeneous;

[0228] (3) Add sodium polyaspartate to the solution and stir until homogeneous;

[0229] (4) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0, and obtain a cleaning agent of the traditional dispersant system.

[0230] Comparative Example 2 (Ordinary non-nano adsorbent system):

[0231] The cleaning agent in this comparative example was obtained by reacting the following raw materials in a percentage by mass:

[0232] 2% aminosulfonic acid;

[0233] Citric acid 10%;

[0234] 3% sodium gluconate;

[0235] Alkyl glycosides 12%;

[0236] 0.5% micron-sized silica;

[0237] pH adjuster 3%;

[0238] Deionized water balance;

[0239] When preparing a cleaning agent based on a common non-nano-adsorbent system, each raw material is added according to the above-mentioned dosage, including the following steps:

[0240] (1) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0241] (2) Add the alkyl glycoside to the solution and stir until homogeneous;

[0242] (3) Slowly add micron-sized silica into the solution and use high-shear or ultrasonic dispersion equipment to fully disperse it so that the particles are uniformly and stably suspended in the solution;

[0243] (4) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0, and obtain a cleaning agent of ordinary non-nano adsorbent system.

[0244] Comparative Example 3 (System without hydrophobic trapping agent):

[0245] The cleaning agent in this comparative example, which is a hydrophobic trapping agent-free system, was obtained by reacting the following raw materials in a percentage by mass:

[0246] 2% aminosulfonic acid;

[0247] Citric acid 10%;

[0248] 3% sodium gluconate;

[0249] Alkyl glycosides 12%;

[0250] TiO2 nanoparticles 0.5%;

[0251] pH adjuster 3%;

[0252] Deionized water balance;

[0253] When preparing a cleaning agent without hydrophobic trapping agents, each raw material is added according to the above-mentioned dosage, including the following steps:

[0254] (1) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0255] (2) Add the alkyl glycoside to the solution and stir until homogeneous;

[0256] (3) Slowly add TiO2 nanoparticles into the solution and use high shear or ultrasonic dispersion equipment to fully disperse them so that the particles are uniformly and stably suspended in the solution;

[0257] (4) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0, and prepare a cleaning agent without hydrophobic trapping agent system.

[0258] Comparative Example 4 (System without surface complexing agent):

[0259] The cleaning agent in this comparative example, which is a surface-complexing agent-free system, was obtained by reacting the following raw materials in a percentage by mass:

[0260] 2% aminosulfonic acid;

[0261] Citric acid 10%;

[0262] 3% sodium gluconate;

[0263] Alkyl glycosides 12%;

[0264] Polydimethylsiloxane 0.5%;

[0265] pH adjuster 3%;

[0266] Deionized water balance;

[0267] When preparing a cleaning agent without surface complexing agents, each raw material is added in the amounts described above, including the following steps:

[0268] (1) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0269] (2) Add the alkyl glycoside to the solution and stir until homogeneous;

[0270] (3) Slowly add polydimethylsiloxane to the solution and use high shear or ultrasonic dispersion equipment to fully disperse it so that the particles are uniformly and stably suspended in the solution;

[0271] (4) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0, and obtain a cleaning agent without surface complexing agent system.

[0272] Comparative Example 5 (System without composite functional nano-adsorbent):

[0273] 2% aminosulfonic acid;

[0274] Citric acid 10%;

[0275] 3% sodium gluconate;

[0276] Alkyl glycosides 12%;

[0277] pH adjuster 3%;

[0278] Deionized water balance;

[0279] When preparing a cleaning agent without a composite functional nano-adsorbent system, each raw material is added according to the above-mentioned dosage, including the following steps:

[0280] (1) While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved;

[0281] (2) Add the alkyl glycoside to the solution and stir until homogeneous;

[0282] (3) Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0, and obtain a cleaning agent without composite functional nano-adsorbent system.

[0283] The effects of the examples and comparative examples were measured:

[0284] (a) Cleaning effect evaluation experiment

[0285] 1. Preparation of experimental materials

[0286] 1.1 Cleaning object: Select glass of the same specifications as the cleaning substrate and weigh the initial weight of the glass.

[0287] 1.2 Simulated Fouling:

[0288] 1.2.1 Analytical grade calcium chloride dihydrate (CaCl2·2H2O) was used to prepare a 5.0 g / L standard hard water solution.

[0289] 1.2.2 Using a pipette, 10 ml of a standard hard water solution was evenly coated onto the cleaned substrate and placed in an oven for drying and aging stabilization for 48 hours. The initial Ca was calculated. 2+ The total mass is 0.01363g.

[0290] 1.2.3 Weigh the glass slide after calcification treatment. Apply hydraulic oil evenly to the glass slide and age it for 48 hours. Weigh the total mass after oiling. The result is:

[0291] Total mass of contaminants = Total mass after oiling - Initial mass of glass;

[0292] Initial oil coating total mass = total mass after oil coating - initial glass mass - 0.01363g;

[0293] 2. Cleaning solution: Prepare a cleaning agent solution according to the examples and comparative examples, and dilute it 30 times to obtain a working solution.

[0294] 3. Obtain the sample to be analyzed: Spray 50ml of working solution onto the contaminated glass substrate and let it act for 10 minutes, then spray with 50ml of deionized water. Collect all cleaning waste liquid to ensure no loss. Dry for 24 hours and weigh to obtain the weight after cleaning.

[0295] 4. Calculation of cleaning efficiency

[0296]

[0297] 5. Experimental Results

[0298] Table 1: Cleaning efficiency data of the examples and comparative examples

[0299]

[0300] 6. Experimental Conclusions

[0301] Cleaning efficiency data show that the cleaning compositions of organic acid synergistic composite nano-adsorbents used in Examples 1-8 can achieve good cleaning effects on scale and oil stains.

[0302] (II) Experiment on the evaluation of the solidification rate of pollutants in waste liquid

[0303] 1. All collected cleaning waste liquid is centrifuged at high speed to separate solid clumps (adsorbent + pollutants) and clear liquid (waste liquid).

[0304] 2. Take 30 ml of the clear liquid and determine the residual dissolved Ca using standard EDTA complexometric titration. 2+ concentration.

[0305] 3. Waste liquid Ca 2+ Calculation of curing rate (curing efficiency of inorganic materials)

[0306]

[0307] Among them, dissolved Ca in the waste liquid 2+ Mass = Dissolved Ca 2+ Concentration × 100ml.

[0308] 4. Take 30 ml of clear liquid, and extract the liquid sample thoroughly with n-hexane using the standard gravimetric method. Evaporate the extract to dryness and weigh the amount of oil residue remaining in the beaker.

[0309] 5. Calculation of waste liquid oil solidification rate (organic matter solidification efficiency)

[0310]

[0311] 6. Experimental Results

[0312] Table 2: Curing rate data for examples and comparative examples

[0313]

[0314] 7. Experimental Conclusions

[0315] (1) Curing rate data show that the cleaning compositions of Examples 1-8 have a curing rate of 0.5% in Ca2+. 2+The curing rate and oil stain curing rate are significantly higher than those of the cleaning agent in the traditional dispersant system of Comparative Example 1. This demonstrates the absolute advantage of the physical curing mechanism of the cleaning composition of this invention in solving secondary pollution of waste liquid. Compared with the passive technical route of traditional chemical dispersion, this invention pioneers a new active removal path of physical curing. Through the action of composite functional nano-adsorbents, the Ca²⁺ released by pollutants during the cleaning process is reduced. + Mg² + Metal ions are instantly solidified by nano-surface complexing agents through coordination; simultaneously, organic pollutants such as grease are efficiently captured by hydrophobic trapping agents through hydrophobic interactions. This ensures that the vast majority of pollutants are firmly fixed inside or on the surface of the adsorbent solid particles during the cleaning stage. Therefore, the content of dissolved and suspended pollutants in the wastewater generated after cleaning is extremely low, eliminating the need for complex secondary chemical treatment processes such as coagulation, sedimentation, and neutralization, thus meeting or even far exceeding environmental emission requirements. This greatly simplifies the post-treatment process and significantly reduces overall cleaning costs and environmental pressure.

[0316] (2) The curing rate data shows that the cleaning agent of Comparative Example 2 with ordinary micron-sized adsorbent has extremely poor curing effect, while the cleaning agent of Comparative Example 3 only has a curing effect in Ca 2+ The curing rate was better than that of the cleaning agent in Comparative Example 4, which only showed better curing rate for oil stains. This proves that TiO2 and modified PDMS are only effective for one type of pollutant, and must be used in combination to achieve the high efficiency of simultaneous curing in Example 2, which reflects the synergistic effect between key components.

[0317] (3) Example 2: The composite functional nano-adsorbent composed of 60% TiO2 + 40% modified PDMS ensures extremely high Ca content. 2+ While achieving a high curing rate, the curing rate of oil stains was also maintained at an optimal level, thus proving that the composite functional nano-adsorbent with a ratio of 60% TiO2:40% modified PDMS achieved the best balance between inorganic complexation and organic capture.

[0318] (4) As can be seen from Examples 2-6, the curing rate of the composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS) is positively correlated when the addition amount is 0.5-1.0%. After the addition amount exceeds 1.0%, the curing rate no longer increases significantly. This proves that the optimal addition amount of the composite functional nano-adsorbent (60% TiO2 + 40% modified PDMS) is 1%.

[0319] (III) Aluminum Alloy Corrosion Rate Measurement Experiment

[0320] 1. Preparation of experimental materials

[0321] Using a standard 50×25×2mm photovoltaic module commonly used 6063 aluminum alloy test piece, a cleaning agent solution was prepared according to the example and comparative examples, and then diluted 30 times to obtain the working solution.

[0322] 2. Corrosion Rate Operation

[0323] 2.1 The test piece was degreased with acetone, rinsed with deionized water, dried, and its initial mass was weighed using a balance with an accuracy of 0.1 mg.

[0324] 2.2 The test piece is suspended and immersed in a sufficient amount of cleaning agent solution and soaked continuously at 40°C for 24 hours.

[0325] 2.3 Remove the test piece, remove any adhering substances from the surface with a brush, rinse with deionized water, and dry. Observe the appearance of the aluminum sheet and weigh the final mass of the test piece.

[0326] 3. Corrosion Rate Calculation

[0327]

[0328] 4. Experimental Results

[0329] Table 3: Corrosion rate data of aluminum alloys in the examples and comparative examples

[0330]

[0331] 5. Experimental Conclusions

[0332] The aluminum alloy corrosion rate data show that the aluminum alloy corrosion rates of Examples 1-8 are significantly lower than those of the cleaning agent in Comparative Example 1 (using a traditional dispersant system) and Comparative Example 5 (using a cleaning agent without composite functional nano-adsorbents). This is mainly because the contaminants are solidified and stably exist in the cleaning solution by the composite functional nano-adsorbents in Examples 1-8 the instant they are generated or peeled off, thus eliminating Ca²⁺ at its source. + Mg² + This eliminates the risk of plasma redeposition and the formation of water stains or secondary mineral scale on clean surfaces. Simultaneously, it effectively prevents the re-adhesion of detached organic contaminants due to loss of dispersion protection. This not only ensures high surface cleanliness and high light transmittance after a single cleaning but also avoids potential damage to the cleaned items caused by repeated contamination and cleaning.

[0333] It should be stated that the above-described specific embodiments are merely preferred embodiments of the present invention and the technical principles employed. Those skilled in the art should understand that various modifications, equivalent substitutions, and variations can be made to the present invention. However, such variations, as long as they do not depart from the spirit of the present invention, should be within the scope of protection of the present invention. Furthermore, some terminology used in this specification and claims is not limiting, but merely for ease of description.

Claims

1. A cleaning composition of an organic acid synergistic composite nano-adsorbent, characterized in that, By mass percentage, it includes the following components: 1%-3% aminosulfonic acid; Citric acid 5%-10%; Sodium gluconate 2%-5%; Alkyl glycosides 5%-20%; Composite functional nano-adsorbents: 0.1%-1.5%; pH adjuster 1%-4%; Deionized water balance; The composite functional nano-adsorbent comprises the following components by mass percentage: Nano-surface complexing agent 50%-80%; Hydrophobic trapping agent 20%-50%; The nano-surface complexing agent is titanium dioxide, and the hydrophobic trapping agent is modified polydimethylsiloxane. The modified polydimethylsiloxane is prepared as follows: H-PDMS prepolymer with an average molecular weight of (10000±5000) g / mol and allyl-terminated polyether with an average molecular weight of (3500±1000) g / mol were added to a reaction vessel at a molar ratio of 1.20:1.00, and an appropriate amount of toluene was added as a solvent. The system was heated to 110℃ under an inert gas atmosphere and kept stable. Platinum catalyst was slowly added dropwise, and after the addition was completed, the reaction was stirred continuously at the reaction temperature for several hours. After the reaction was completed, the solvent and low molecular weight volatiles were removed by vacuum distillation to obtain modified polydimethylsiloxane. The preparation method of the composite functional nano-adsorbent is as follows: The nano-surface complexing agent and the hydrophobic trapping agent were dried in a vacuum drying oven at 80℃ for 4-6 hours. The dried nano-surface complexing agent and the hydrophobic trapping agent were placed in a high-speed mixer and stirred at 500-1000 rpm for 15 minutes. The premixed powder was transferred to a high-energy ball mill for high-energy ball milling for 1-3 hours at a speed of 300-600 rpm. The composite powder was sieved through a 100-150 mesh standard sieve to remove agglomerates or large particles, thus obtaining the composite functional nano-adsorbent.

2. The cleaning composition of the organic acid synergistic composite nano-adsorbent according to claim 1, characterized in that, By mass percentage, it includes the following components: 2% aminosulfonic acid; Citric acid 10%; 3% sodium gluconate; Alkyl glycosides 12%; Composite functional nano-adsorbent 1%; pH adjuster 3%; Deionized water balance.

3. The cleaning composition of the organic acid synergistic composite nano-adsorbent according to claim 1, characterized in that, The pH adjuster is one or more of sodium hydroxide and potassium hydroxide.

4. A method for preparing a cleaning composition of an organic acid synergistic composite nano-adsorbent according to any one of claims 1-3, characterized in that, Includes the following steps: S1. Preparation of composite functional nano-adsorbents; S2. While stirring, add aminosulfonic acid, citric acid and sodium gluconate to deionized water and stir until completely dissolved; S3. Add the alkyl glycoside to the solution and stir until homogeneous; S4. Slowly add the composite functional nano-adsorbent into the solution and use a high-shear or ultrasonic dispersion device to fully disperse it so that the adsorbent particles are uniformly and stably suspended in the solution. S5. Add a pH adjuster to the solution to precisely control the pH value of the composition at 3.0~4.0 to obtain a clean composition.

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