Photocatalytic self-cleaning detergent and preparation method thereof

Abstract

The invention discloses a photocatalytic self-cleaning detergent and a preparation method thereof, and the photocatalytic self-cleaning detergent comprises the following components by weight: 5-10 parts of a TiO2-zeolite compound; 2 to 3 parts of parachlorometaxylenol; 5-8 parts of sodium citrate; 3-5 parts of sodium silicate; 1 to 2 parts of polyvinylpyrrolidone; 20 to 30 parts of a surfactant; 0.2-1 part of an enzyme preparation; 2-3 parts of a pH regulator; and 50-70 parts of water. According to the photocatalytic self-cleaning detergent disclosed by the invention, the absorption of ultraviolet rays is promoted through PCMX, so that the TiO2-zeolite compound is excited to generate active oxygen with strong oxidizing property, the degradation efficiency of the detergent on stubborn organic stains is improved, and the problems that TiO2 is poor in dispersity in the detergent and the illumination activation is limited are solved; stable release of the photocatalytic material in the washing process is achieved, the continuous and efficient cleaning effect is ensured, and the method can be applied to hospitals or industries and other scenes needing large-scale and deep cleaning.

Description

Technical Field

[0001] The present invention relates to the technical field of detergents, and in particular to a photocatalytic self-cleaning detergent and a preparation method thereof. Background Art

[0002] Traditional detergent systems mainly rely on the synergistic effect of chemical surfactants and biological enzymes to achieve stain removal. However, they have obvious limitations when dealing with organic stains such as grease, protein (such as blood stains) and pigments. More seriously, the long-term use of large amounts of chemical surfactants can easily lead to environmental problems such as eutrophication of water bodies. Although TiO2 materials based on semiconductor photocatalytic principles can produce strong oxidizing active oxygen through light excitation to achieve organic degradation, in actual applications, nanoparticles are prone to agglomeration and deactivation, resulting in a sharp drop in catalytic efficiency. Although studies have attempted to improve their dispersibility and cyclic stability through porous material loading strategies such as zeolite molecular sieves, this technology has not yet been successfully integrated into the formulation system of commercial detergents due to the complexity of the solidification process and the limitations of the light response range. Therefore, the development of new photocatalytic self-cleaning detergents that have both high-efficiency decontamination and environmentally friendly properties has become an important research direction in the current field of green chemistry and cleaning technology. Summary of the Invention

[0003] The purpose of the present invention is to provide a photocatalytic self-cleaning detergent and a preparation method thereof to address the deficiencies of the prior art and to solve the problems raised in the background art.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In one aspect, the present invention provides a photocatalytic self-cleaning detergent comprising the following components in parts by weight:

[0006]

[0007] As a preferred embodiment of the photocatalytic self-cleaning detergent, the following components are included in parts by weight:

[0008]

[0009] As a preferred embodiment of the photocatalytic self-cleaning detergent, the enzyme preparation is one or more of protease and lipase.

[0010] As a preferred embodiment of the photocatalytic self-cleaning detergent, the surfactant is sodium dodecylbenzenesulfonate, and the pH regulator is sodium carbonate.

[0011] In another aspect, the present invention provides a method for preparing a photocatalytic self-cleaning detergent, comprising the following steps:

[0012] S1, preparing TiO2-zeolite composite;

[0013] S2, grinding the TiO2-zeolite composite and polyvinyl pyrrolidone in a ball mill for 20 min to reduce the particle size to <10 μm;

[0014] S3, transfer the premixed material in the ball mill to a stirring container, add a surfactant, and stir for 10-15 minutes to fully mix the surfactant and the premixed material;

[0015] S4. Add sodium citrate and sodium silicate to a stirring container in sequence and stir for 10-15 minutes to uniformly disperse them in the system;

[0016] S5. Add the enzyme preparation to the stirring container and stir for 30 minutes;

[0017] S6. Add parachloro-meta-xylenol to the stirring container and stir for 10 minutes to form a uniform mixture;

[0018] S7. Measure the pH value of the mixture, slowly add a pH regulator according to the measurement result and continuously stir to maintain the pH value of the system between 9 and 10, thereby preparing a photocatalytic self-cleaning detergent.

[0019] As a preferred embodiment of the method for preparing a photocatalytic self-cleaning detergent, step S1 specifically comprises:

[0020] S11. Tetrabutyl titanate and ethanol were mixed in a volume ratio of 1:3, and ethanol was slowly added dropwise while stirring at 200-300 rpm. Stirring was continued for 15-20 minutes after the addition of ethanol was completed. Deionized water was then slowly added dropwise and the pH was adjusted to 3-4 with hydrochloric acid. After the solution became turbid, stirring was continued for 30-60 minutes to form a sol;

[0021] S12, calcining rice husk ash at 600-700°C for 2-3 hours to remove organic matter, then treating with 1 mL of hydrochloric acid at 80°C for 2 hours, washing until neutral, and drying; then mixing the treated rice husk ash with metakaolin at a ratio of SiO2 / Al2O3=4, and adding water to form a slurry; then transferring the slurry to a reactor, hydrothermally reacting at 120°C for 6 hours, and finally washing and drying the product to obtain FAU-type zeolite;

[0022] S13. Immerse the FAU zeolite in the sol and stir for 6-8 hours. Then take out the FAU zeolite, rinse it with deionized water, and dry it at 80°C for 12-15 hours. Then, heat it to 450°C in a muffle furnace at 2-3°C / min and calcine it for 2 hours to obtain a TiO2-zeolite composite.

[0023] Beneficial effects of the present invention:

[0024] The present invention uses rice husk ash and metakaolin to prepare a TiO2-zeolite composite, and applies the TiO2-zeolite composite to detergents. The unique three-dimensional porous structure of the TiO2-zeolite composite can adsorb organic molecules such as oleic acid and hemoglobin. At the same time, the abundant silanol groups on the zeolite surface can form chemical anchors with TiO2, increasing the dispersion of nanoparticles to more than 85%, effectively inhibiting agglomeration and inactivation. In addition, the TiO2-zeolite composite can generate highly oxidizing active oxygen through ultraviolet excitation, which can degrade organic matter. The composite remaining after washing can also continue to decompose residual organic matter in fabrics under natural light, thereby achieving a self-cleaning function.

[0025] At the same time, the present invention also adds PCMX to the detergent. PCMX can promote the absorption of ultraviolet rays by the detergent. The TiO2-zeolite complex can produce more active oxygen under the excitation of ultraviolet rays, thereby improving the degradation efficiency of the detergent on stubborn organic stains. It solves the problems of poor dispersion of TiO2 in detergents and limited light activation, realizes the stable release of photocatalytic materials during the washing process, and ensures continuous and efficient cleaning effects. It can be used in scenarios such as hospitals or industries that require large-scale and deep cleaning. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments of the present invention. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0027] Figure 1 This is a comparison chart of the cleaning effects of sesame oil-stained pieces after being cleaned by Example 1 of the present invention and Comparative Examples 1-4.

[0028] Figure 2 This is a comparison chart of the effects of cleaning pig blood stains after Example 1 of the present invention and Comparative Examples 1-4.

[0029] Figure 3 This is a comparison chart of the effects of cleaning red dye-stained pieces after being cleaned by Example 1 of the present invention and Comparative Examples 1-4. DETAILED DESCRIPTION

[0030] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific implementation methods.

[0031] Among them, the drawings are only used for illustrative purposes and represent only schematic diagrams rather than actual pictures, and should not be understood as limiting this patent; in order to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of the actual product; for those skilled in the art, it is understandable that some well-known structures and their descriptions in the drawings may be omitted.

[0032] The same or similar numbers in the drawings of the embodiments of the present invention correspond to the same or similar parts; in the description of the present invention, it should be understood that if the terms "upper", "lower", "left", "right", "inside", "outside" and the like indicate an orientation or position relationship based on the orientation or position relationship shown in the drawings, it is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation. Therefore, the terms describing the position relationship in the drawings are only used for illustrative purposes and cannot be understood as limiting this patent. For ordinary technicians in this field, the specific meanings of the above terms can be understood according to specific circumstances.

[0033] In the description of the present invention, unless otherwise expressly specified or limited, when the term "connection" or the like appears to indicate a connection relationship between components, such term should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be internal communication between two components or an interaction between two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood in specific circumstances.

[0034] Example 1:

[0035] The photocatalytic self-cleaning detergent of this embodiment is obtained by reacting the following raw materials in parts by weight:

[0036]

[0037] When preparing the photocatalytic self-cleaning detergent, the raw materials are added according to the above-mentioned addition amounts, which includes the following steps:

[0038] (1) Preparation of TiO2-zeolite composite;

[0039] Tetrabutyl titanate and ethanol were mixed in a volume ratio of 1:3, and ethanol was slowly added dropwise under stirring at 200-300 rpm. Stirring was continued for 15-20 minutes after the addition of ethanol was completed. Deionized water was then slowly added dropwise and the pH was adjusted to 3-4 with hydrochloric acid. After the solution became turbid, stirring was continued for 30-60 minutes to form a sol;

[0040] The rice husk ash was calcined at 600-700°C for 2-3 hours to remove organic matter, then treated with 1 mL of hydrochloric acid at 80°C for 2 hours, washed until neutral, and dried. The treated rice husk ash was then mixed with metakaolin at a ratio of SiO2 / Al2O3 = 4, and water was added to form a slurry. The slurry was then transferred to a reactor and hydrothermally reacted at 120°C for 6 hours. The product was finally washed and dried to obtain FAU-type zeolite.

[0041] The FAU zeolite was immersed in the sol and stirred for 6-8 hours. The FAU zeolite was then taken out and rinsed with deionized water and dried at 80°C for 12-15 hours. The temperature was then increased to 450°C in a muffle furnace at 2-3°C / min and calcined for 2 hours to obtain a TiO2-zeolite composite.

[0042] (2) The TiO2-zeolite composite and polyvinylpyrrolidone were placed in a ball mill and ground at a speed of 120 r / min for 20 min to reduce the particle size to <10 μm;

[0043] During the ball milling process, the machine can be stopped at appropriate times to check the mixing and grinding effects, and the ball milling parameters can be adjusted according to the actual situation.

[0044] (3) transferring the premixed material in the ball mill to a stirring container, adding sodium dodecylbenzene sulfonate, and stirring at a speed of 2000 r / min for 10-15 min to fully mix the sodium dodecylbenzene sulfonate and the premixed material;

[0045] (4) Sodium citrate and sodium silicate were added to a stirring container in sequence and stirred at a speed of 2000 r / min for 10-15 min to uniformly disperse them in the system;

[0046] During the stirring process, pay attention to the uniformity and fluidity of the system and make timely adjustments if any abnormalities are found.

[0047] (5) Add protease and lipase to a stirring container and stir at 2000 r / min for 30 min to allow the enzyme preparation to fully contact and mix with other ingredients to form a uniform mixture;

[0048] (6) adding parachlorometaxylenol to a stirring vessel and stirring at a speed of 2000 r / min for 10 min to form a uniform mixture;

[0049] (7) Using a pH meter to measure the pH value of the mixture, sodium carbonate was slowly added according to the measurement result while stirring continuously to maintain the pH value of the system between 9 and 10, thereby preparing a photocatalytic self-cleaning detergent.

[0050] Comparative Example 1:

[0051] The photocatalytic self-cleaning detergent of this embodiment is obtained by reacting the following raw materials in parts by weight:

[0052]

[0053] When preparing the photocatalytic self-cleaning detergent, the raw materials are added according to the above-mentioned addition amounts, which includes the following steps:

[0054] (1) Preparation of TiO2-zeolite composite;

[0055] Tetrabutyl titanate and ethanol were mixed in a volume ratio of 1:3, and ethanol was slowly added dropwise under stirring at 200-300 rpm. Stirring was continued for 15-20 minutes after the addition of ethanol was completed. Deionized water was then slowly added dropwise and the pH was adjusted to 3-4 with hydrochloric acid. After the solution became turbid, stirring was continued for 30-60 minutes to form a sol;

[0056] The rice husk ash was calcined at 600-700°C for 2-3 hours to remove organic matter, then treated with 1 mL of hydrochloric acid at 80°C for 2 hours, washed until neutral, and dried. The treated rice husk ash was then mixed with metakaolin at a ratio of SiO2 / Al2O3 = 4, and water was added to form a slurry. The slurry was then transferred to a reactor and hydrothermally reacted at 120°C for 6 hours. The product was finally washed and dried to obtain FAU-type zeolite.

[0057] The FAU zeolite was immersed in the sol and stirred for 6-8 hours. The FAU zeolite was then taken out and rinsed with deionized water and dried at 80°C for 12-15 hours. The temperature was then increased to 450°C in a muffle furnace at 2-3°C / min and calcined for 2 hours to obtain a TiO2-zeolite composite.

[0058] (2) The TiO2-zeolite composite and polyvinylpyrrolidone were placed in a ball mill and ground at a speed of 120 r / min for 20 min to reduce the particle size to <10 μm;

[0059] During the ball milling process, the machine can be stopped at appropriate times to check the mixing and grinding effects, and the ball milling parameters can be adjusted according to the actual situation.

[0060] (3) transferring the premixed material in the ball mill to a stirring container, adding sodium dodecylbenzene sulfonate, and stirring at a speed of 2000 r / min for 10-15 min to fully mix the sodium dodecylbenzene sulfonate and the premixed material;

[0061] (4) Sodium citrate and sodium silicate were added to a stirring container in sequence and stirred at a speed of 2000 r / min for 10-15 min to uniformly disperse them in the system;

[0062] During the stirring process, pay attention to the uniformity and fluidity of the system and make timely adjustments if any abnormalities are found.

[0063] (5) Add protease and lipase to a stirring container and stir at 2000 r / min for 30 min to allow the enzyme preparation to fully contact and mix with other ingredients to form a uniform mixture;

[0064] (6) The pH value of the mixture was measured using a pH meter. Sodium carbonate was slowly added according to the measurement result while stirring continuously to maintain the pH value of the system between 9 and 10, thereby preparing a photocatalytic self-cleaning detergent that did not contain PCMX.

[0065] Comparative Example 2:

[0066] The detergent of this embodiment is obtained by reacting the following raw materials in parts by weight:

[0067]

[0068]

[0069] When preparing the detergent, the raw materials are added according to the above-mentioned addition amounts, including the following steps:

[0070] (1) Place polyvinyl pyrrolidone in a ball mill and grind at a speed of 120 r / min for 20 min to reduce the particle size to <10 μm;

[0071] During the ball milling process, the machine can be stopped at appropriate times to check the grinding effect and the ball milling parameters can be adjusted according to the actual situation.

[0072] (2) transferring the material in the ball mill to a stirring container, adding sodium dodecylbenzenesulfonate, and stirring at a speed of 2000 r / min for 10-15 min to fully mix the sodium dodecylbenzenesulfonate with the material;

[0073] (3) Sodium citrate and sodium silicate were added to a stirring container in sequence and stirred at a speed of 2000 r / min for 10-15 minutes to uniformly disperse them in the system;

[0074] During the stirring process, pay attention to the uniformity and fluidity of the system and make timely adjustments if any abnormalities are found.

[0075] (4) Add protease and lipase to a stirring container and stir at 2000 r / min for 30 min to allow the enzyme preparation to fully contact and mix with other ingredients to form a uniform mixture;

[0076] (5) adding parachlorometaxylenol to a stirring vessel and stirring at a speed of 2000 r / min for 10 min to form a uniform mixture;

[0077] (6) Using a pH meter to measure the pH value of the mixture, sodium carbonate was slowly added according to the measurement result while stirring continuously to maintain the pH value of the system between 9 and 10, thereby preparing a detergent free of TiO2-zeolite complex.

[0078] Comparative Example 3:

[0079] The detergent of this embodiment is obtained by reacting the following raw materials in parts by weight:

[0080]

[0081] When preparing the detergent, the raw materials are added according to the above-mentioned addition amounts, including the following steps:

[0082] (1) Place polyvinyl pyrrolidone in a ball mill and grind at a speed of 120 r / min for 20 min to reduce the particle size to <10 μm;

[0083] During the ball milling process, the machine can be stopped at appropriate times to check the grinding effect and the ball milling parameters can be adjusted according to the actual situation.

[0084] (2) transferring the material in the ball mill to a stirring container, adding sodium dodecylbenzenesulfonate, and stirring at a speed of 2000 r / min for 10-15 min to fully mix the sodium dodecylbenzenesulfonate with the material;

[0085] (3) Sodium citrate and sodium silicate were added to a stirring container in sequence and stirred at a speed of 2000 r / min for 10-15 minutes to uniformly disperse them in the system;

[0086] During the stirring process, pay attention to the uniformity and fluidity of the system and make timely adjustments if any abnormalities are found.

[0087] (4) Add protease and lipase to a stirring container and stir at 2000 r / min for 30 min to allow the enzyme preparation to fully contact and mix with other ingredients to form a uniform mixture;

[0088] (5) Using a pH meter to measure the pH value of the mixture, sodium carbonate was slowly added according to the measurement result while stirring continuously to maintain the pH value of the system between 9 and 10, thereby preparing a detergent free of TiO2-zeolite complex and PCMX.

[0089] Comparative Example 4:

[0090] The detergent in this embodiment is a standard detergent formulated in accordance with Appendix B of the national standard GB / T 13174-2021 "Determination of detergency and cyclic washing performance of detergents for clothing."

[0091] The effects of the embodiments and comparative examples were measured:

[0092] 1. Detergency test:

[0093] 1.1 Production of dirty cloth:

[0094] 1.1.1 Cut standard white cotton cloth into 6cm*6cm square pieces and wash them in a washing machine using the standard cycle (total washing time is 51 minutes, including one 13-minute main wash, two rinses, and one 5-minute spin cycle).

[0095] 1.1.2 After washing, take out the cloth, place it in a suitable container, and wash it with deionized water at 60°C for 30 minutes.

[0096] 1.1.3 After washing again, take out the cloth, spin dry it, and iron it flat with an electric iron for later use.

[0097] 1.1.4 Thoroughly soak the cloth prepared in 1.1.3 in the dirty liquid (the dirty liquids are divided into three groups: grease, blood, and dye. Grease is represented by sesame oil; blood is represented by pig blood; and dye is represented by red dye). If the cloth is not fully soaked, apply pressure to the cloth. After 20 minutes, remove the cloth and air dry it at room temperature before use. If the cloth has wrinkles, iron it with an electric iron to smooth them out.

[0098] 1.2 Test steps

[0099] 1.2.1 Example 1 and Comparative Examples 1-3 were used as the experimental group, and Comparative Example 4 was used as the control group. Four blank cloth pieces prepared in 1.1.3 were taken from each group. The whiteness values ​​of the two diagonal lines of each blank cloth piece were measured according to the method of standard GB / T 13174-2021. 16 data points were obtained for each group, recorded as F0.

[0100] 1.2.2 Prepare the cloth piece with the initial whiteness value measured in 1.2.1 into a dirty piece for experiment according to the steps in 1.1.4. Measure the whiteness value of the cloth piece again and record it as F1.

[0101] 1.2.3 Washing tests were conducted in groups within a vertical decontamination machine, with UV light irradiation activated throughout the entire wash test. Prior to measurement, the impeller, working tank, and decontamination bathtub were individually numbered and fixed to form a "working unit." During the test, 1 L of a test solution (0.2% concentration, unless otherwise specified) prepared with the detergents from Example 1 and Comparative Examples 1-4 was poured into the corresponding decontamination bathtub using 250 mg / kg hard water (preheated to approximately 30°C). The bathtub was placed in the designated position and the impeller installed. The instrument was adjusted to maintain a wash test temperature of 30°C ± 1°C, and the test was then prepared.

[0102] 1.2.4 Put the dirty pieces in 1.2.2 into the bathtub, start stirring, and maintain the stirring speed at 120r / min. The washing process lasts for 20 minutes and then stops.

[0103] 1.2.5 Take out the test piece from the decontamination bathtub, put it into the inner barrel of the rinser, spin dry for 15 seconds (the speed of the inner barrel is about 1800r / min), and control the water. Then pour 1500mL of tap water into the rinser and replace the lid. Rinse the test piece at a constant speed for 30 seconds in a manner of 5 clockwise and 5 counterclockwise rotations. During this period, the inner barrel should be fully rotated, but it is necessary to avoid overflow of the rinse water in the container due to too fast rotation. Drain the rinse water and manually dehydrate the test piece for 15 seconds. Add 1500mL of tap water again, repeat the second rinse and dehydration, and repeat this for a total of four times. After the last rinse and dehydration, take out the test piece and place it in an enamel tray to dry at room temperature, and then measure the whiteness F2 (the experimental results can be referred to Figures 1 to 3 ).

[0104] 2. Detergency test data

[0105] 2.1 Calculation of stain removal rate:

[0106]

[0107] Where i is the i-th type of dirty cloth test piece; F 0i -F 1i F is the whiteness value of the i-th type of dirty cloth specimen stained with the experimental stain; 2i -F 1i is the whiteness value of the i-th type of dirty cloth test piece after the experimental stain is washed off; the result is rounded to one decimal place.

[0108] 2.2 Calculation of the stain removal rate ratio relative to standard detergent:

[0109]

[0110] In the formula is the stain removal rate of the experimental samples in the experimental group; The stain removal rate of the standard detergent experiment for the control group; the result is rounded to one decimal place.

[0111] 2.3 Experimental data

[0112] 2.3.1 Experimental data of standard detergents

[0113] Table 1: Whiteness value change table of experimental cloth pieces of comparative example 4 standard detergent

[0114]

[0115]

[0116] 2.3.2 Experimental data of Example 1

[0117] Table 2: Whiteness value change table of the experimental cloth pieces of the photocatalytic self-cleaning detergent in Example 1

[0118]

[0119] Table 3: Experimental stain removal rate ratio table of Example 1

[0120]

[0121]

[0122] It can be seen from Table 3 that in the detergency test of the photocatalytic self-cleaning detergent of Example 1 and the standard detergent of Comparative Example 4, the removal rate of the detergent of Example 1 for different organic stains such as grease, blood stains, and dyes is significantly higher than that of Comparative Example 4. This shows that the photocatalytic self-cleaning detergent of this embodiment can effectively improve the decontamination effect.

[0123] 2.3.3 Experimental data of comparative example 1

[0124] Table 4: Whiteness value change table of experimental cloth pieces without PCMX detergent in comparative example 1

[0125]

[0126] Table 5: Experimental stain removal rate ratio table of comparative example 1

[0127] Name of dirty cloth <![CDATA[Removal rate ratio (P i )]]> sesame oil 1.9 pig blood 2.2 Red Dye 2.2

[0128] It can be seen from Tables 3 and 5 that in the detergency experiment of the photocatalytic self-cleaning detergent containing PCMX in Example 1 and the detergent not containing PCMX in Comparative Example 1, the removal rate ratio of the detergent in Example 1 for different organic stains such as grease, blood stains, and dyes is significantly higher than the removal rate ratio of Comparative Example 1, which proves that PCMX raw materials play an important role in detergents and can help detergents improve their decontamination effect.

[0129] 2.3.4 Experimental data of comparative example 2

[0130] Table 6: Whiteness value change table of experimental cloth pieces without TiO2-zeolite composite detergent in comparative example 2

[0131]

[0132] Table 7: Experimental stain removal rate ratio table of comparative example 2

[0133] Name of dirty cloth <![CDATA[Removal rate ratio (P i )]]> sesame oil 1.3 pig blood 1.3 Red Dye 1.3

[0134] As can be seen from Tables 3 and 7, in the detergency test of the photocatalytic self-cleaning detergent containing the TiO2-zeolite composite in Example 1 and the detergent not containing the TiO2-zeolite composite in Comparative Example 2, the removal rate ratio of the detergent in Example 1 for different organic stains such as grease, blood stains, and dyes is significantly higher than that of Comparative Example 2. This proves that the TiO2-zeolite composite plays an important role in detergents. The key lies in the unique three-dimensional porous structure of the TiO2-zeolite composite made from rice husk ash and metakaolin, which adsorbs organic molecules such as oleic acid and hemoglobin. At the same time, the abundant silanol groups on the surface of the zeolite form a chemical anchor with TiO2, increasing the dispersion of the nanoparticles to more than 85%, effectively inhibiting agglomeration and inactivation, and the TiO2-zeolite composite can generate highly oxidizing active oxygen through ultraviolet excitation. The active oxygen can degrade organic matter. The residual composite after washing can also continue to decompose residual organic matter in the fabric under natural light, thereby achieving a self-cleaning function.

[0135] 2.3.5 Experimental data of comparative example 3

[0136] Table 8: Whiteness value change table of the experimental cloth pieces of detergent without TiO2-zeolite composite and PCMX in Comparative Example 3

[0137]

[0138]

[0139] Table 9: Stain removal rate ratio table of comparative example 3

[0140] Name of dirty cloth <![CDATA[Removal rate ratio (P i )]]> sesame oil 1.0 pig blood 1.3 Red Dye 1.0

[0141] It can be seen from Tables 3, 5, 7 and 9 that in the detergency test of the photocatalytic self-cleaning detergent containing TiO2-zeolite composite and PCMX in Example 1, the detergent without PCMX in Comparative Example 1, and the detergent without TiO2-zeolite composite in Comparative Example 2, the removal rate ratios of the detergents in Example 1 and Comparative Examples 1-2 for different organic stains such as grease, blood stains, and dyes are significantly higher than the removal rate ratio of Comparative Example 3. This proves that adding TiO2-zeolite composite and PCMX raw materials to detergents can effectively improve the decontamination effect.

[0142] 3. UV absorption experiment

[0143] 3.1 Solution preparation: Accurately weigh 2 g of the detergents of Example 1 and Comparative Example 1, respectively, and place them into two 1 L volumetric flasks. Add an appropriate amount of tap water, mix thoroughly, and dilute to the mark.

[0144] 3.2 Take two clean quartz cuvettes, add appropriate amount of preparation solution, place them in a UV spectrophotometer, set the UV region (200-400nm), perform spectral scanning on the two solutions, and obtain their absorbance at different wavelengths.

[0145] 3.3 Experimental data:

[0146] Table 10: Absorbance of Example 1 and Comparative Example 1

[0147]

[0148]

[0149] 3.4 Experimental results analysis:

[0150] As can be seen from Table 10, in the ultraviolet absorption experiment of the photocatalytic self-cleaning detergent containing PCMX in Example 1 and the photocatalytic self-cleaning detergent not containing PCMX in Comparative Example 1, the absorbance of the detergent in Example 1 in the ultraviolet region of 200-400nm was significantly higher than that of the detergent in Comparative Example 1. This proves that the PCMX raw material added in Example 1 not only exerts an antibacterial effect, but also PCMX significantly enhances the absorption of ultraviolet rays by the detergent;

[0151] From this, we can know that the reason why PCMX can improve the decontamination effect of detergents is mainly because PCMX promotes the absorption of ultraviolet rays by detergents. The TiO2-zeolite complex produces more active oxygen under the excitation of ultraviolet rays, thereby improving the degradation efficiency of detergents on stubborn organic stains. It solves the problems of poor dispersion of TiO2 in detergents and limited light activation, realizes the stable release of photocatalytic materials during the washing process, and ensures continuous and efficient cleaning effects. It can be used in scenarios such as hospitals or industries that require large-scale and deep cleaning.

[0152] It should be noted that the above-described specific embodiments are merely preferred embodiments of the present invention and the technical principles employed. Those skilled in the art will appreciate that various modifications, equivalent substitutions, and variations may be made to the present invention. However, as long as these modifications do not depart from the spirit of the present invention, they are intended to be within the scope of protection of the present invention. Furthermore, certain terms used in the specification and claims of this application are not intended to be limiting and are provided solely for ease of description.

Claims

1. A photocatalytic self-cleaning detergent, characterized in that: Calculated by weight, it includes the following components:

2. The photocatalytic self-cleaning detergent according to claim 1, characterized in that Calculated by weight, it includes the following components:

3. The photocatalytic self-cleaning detergent according to claim 1, characterized in that The enzyme preparation is one or more of protease and lipase.

4. The photocatalytic self-cleaning detergent according to claim 2, characterized in that The surfactant is sodium dodecylbenzenesulfonate, and the pH regulator is sodium carbonate.

5. A method for preparing a photocatalytic self-cleaning detergent, characterized in that: The following steps are involved: S1, preparing TiO2-zeolite composite; S2, grinding the TiO2-zeolite composite and polyvinyl pyrrolidone in a ball mill for 20 min to reduce the particle size to <10 μm; S3, transfer the premixed material in the ball mill to a stirring container, add a surfactant, and stir for 10-15 minutes to fully mix the surfactant and the premixed material; S4. Add sodium citrate and sodium silicate to a stirring container in sequence and stir for 10-15 minutes to uniformly disperse them in the system; S5. Add the enzyme preparation to the stirring container and stir for 30 minutes; S6. Add parachloro-meta-xylenol to the stirring container and stir for 10 minutes to form a uniform mixture; S7. Measure the pH value of the mixture, slowly add a pH regulator according to the measurement result and continuously stir to maintain the pH value of the system between 9 and 10, thereby preparing a photocatalytic self-cleaning detergent.

6. The method for preparing the photocatalytic self-cleaning detergent according to claim 5, characterized in that: Step S1 specifically includes: S11. Tetrabutyl titanate and ethanol were mixed in a volume ratio of 1:3, and ethanol was slowly added dropwise while stirring at 200-300 rpm. Stirring was continued for 15-20 minutes after the addition of ethanol was completed. Deionized water was then slowly added dropwise and the pH was adjusted to 3-4 with hydrochloric acid. After the solution became turbid, stirring was continued for 30-60 minutes to form a sol; S12, calcining rice husk ash at 600-700°C for 2-3 hours to remove organic matter, then treating with 1 mL of hydrochloric acid at 80°C for 2 hours, washing until neutral, and drying; then mixing the treated rice husk ash with metakaolin at a ratio of SiO2 / Al2O3=4, and adding water to form a slurry; then transferring the slurry to a reactor, hydrothermally reacting at 120°C for 6 hours, and finally washing and drying the product to obtain FAU-type zeolite; S13. Immerse the FAU zeolite in the sol and stir for 6-8 hours. Then take out the FAU zeolite, rinse it with deionized water, and dry it at 80°C for 12-15 hours. Then, heat it to 450°C in a muffle furnace at 2-3°C / min and calcine it for 2 hours to obtain a TiO2-zeolite composite.

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