Photocatalytic self-cleaning detergent and method for preparing the same

Abstract

The application discloses a kind of photocatalytic self-cleaning detergent and preparation method thereof, by weight parts, including the following components: TiO2-zeolite complex 5-10 parts;Para-chloro-m-xylene phenol 2-3 parts;Sodium citrate 5-8 parts;Sodium silicate 3-5 parts;Polyvinylpyrrolidone 1-2 parts;Surfactant 20-30 parts;Enzyme preparation 0.2-1 part;pH regulator 2-3 parts;Water 50-70 parts.The photocatalytic self-cleaning detergent of the application promotes the absorption of ultraviolet light by PCMX, thereby exciting TiO2-zeolite complex to generate strong oxidative active oxygen, improving the degradation efficiency of the detergent on stubborn organic stains, solving the problem of poor dispersibility of TiO2 in the detergent and limited photoactivation, realizing the stable release of photocatalytic materials in the washing process, ensuring sustained and efficient cleaning effect, and can be applied to hospitals or industrial and other scenes requiring a large amount of deep cleaning.

Description

TECHNICAL FIELD

[0001] The present application relates to the detergent technical field, specifically to a kind of photocatalytic self-cleaning detergent and preparation method thereof. BACKGROUND

[0002] Traditional detergent system mainly relies on the synergistic effect of chemical surfactant and biological enzyme to realize stain removal, however, there are obvious limitations in dealing with grease, protein (such as blood stains) and pigment organic stains. More seriously, long-term use of a large number of chemical surfactants can easily cause water eutrophication and other environmental problems. Although TiO2 material based on semiconductor photocatalytic principle can generate strong oxidizing active oxygen to realize organic matter degradation through light excitation, in practical application, nanoparticles are easy to aggregate and deactivate, resulting in a sharp decrease in catalytic efficiency. Although there have been attempts to improve its dispersibility and cycle stability through porous material loading strategies such as zeolite molecular sieve, due to the complexity of the loading process and the limitation of the light response range, this technology has not been successfully integrated into the formula system of commercial detergents. Therefore, developing a new type of photocatalytic self-cleaning detergent with high efficient stain removal and environmental friendly characteristics has become an important research direction in the field of green chemistry and cleaning technology. SUMMARY

[0003] The present application aims at the deficiencies of the prior art, and provides a kind of photocatalytic self-cleaning detergent and preparation method thereof, to solve the problems raised in the background art.

[0004] To achieve this purpose, the technical scheme adopted by the present application is as follows:

[0005] On the one hand, the present application provides a kind of photocatalytic self-cleaning detergent, by weight, including the following components:

[0006]

[0007] As a preferred scheme of photocatalytic self-cleaning detergent, by weight, including the following components:

[0008]

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

[0010] As a preferred scheme of photocatalytic self-cleaning detergent, the surfactant is sodium dodecyl benzene sulfonate, and the pH regulator is sodium carbonate.

[0011] On the other hand, the present application provides a preparation method of photocatalytic self-cleaning detergent, comprising the following steps:

[0012] S1, preparing TiO2-zeolite composite;

[0013] S2, the TiO2-zeolite compound and polyvinylpyrrolidone are put into a ball mill for grinding for 20 min, and the particle size is reduced to <10 mu m;

[0014] S3, the premixed material in the ball mill is transferred to a stirring container, and a surfactant is added, and stirred for 10-15 min, so that the surfactant is fully mixed with the premixed material;

[0015] S4, sodium citrate and sodium silicate are sequentially added in the stirring container, and stirred for 10-15 min, so that they are uniformly dispersed in the system;

[0016] S5, enzyme preparation is added in the stirring container, and stirred for 30 min;

[0017] S6, p-chloro-m-xylene phenol is added in the stirring container, and stirred for 10 min, to form a uniform mixture;

[0018] S7, the pH value of the mixture is measured, and a pH adjuster is slowly added according to the measurement result and continuously stirred, so that the pH value of the system is maintained between 9-10, to prepare the photocatalytic self-cleaning detergent.

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

[0020] S11, tetrabutyl titanate is mixed with ethanol at a volume ratio of 1:3, and under the stirring of 200-300 rpm, ethanol is slowly added dropwise, and after the dropwise addition of ethanol is completed, stirring is continued for 15-20 min, then deionized water is slowly added dropwise, and hydrochloric acid is used to adjust the pH to 3-4, and after the solution becomes turbid, stirring is continued for 30-60 min to form a sol;

[0021] S12, rice husk ash is calcined at 600-700 DEG C for 2-3 h to remove organic matter, and then treated with 1 mL of hydrochloric acid at 80 DEG C for 2 h, washed to neutral and dried; then the treated rice husk ash is mixed with metakaolin at a ratio of SiO2 / Al2O3=4, and water is added to prepare a slurry; then the slurry is transferred to a reaction kettle, and hydrothermal reaction is carried out at 120 DEG C for 6 h, and finally the product is washed and dried to obtain a FAU type zeolite;

[0022] S13, the FAU type zeolite is immersed in the sol, and stirred for 6-8 h, then the FAU type zeolite is taken out and washed with deionized water, and dried at 80 DEG C for 12-15 h; then the temperature is increased to 450 DEG C at a rate of 2-3 DEG C / min in a muffle furnace, and calcined for 2 h, to obtain a TiO2-zeolite compound.

[0023] The beneficial effects of the present application are:

[0024] The application adopts rice husk ash and metakaolin to prepare TiO2-zeolite compound, and applies the TiO2-zeolite compound in a detergent, the unique three-dimensional porous structure of the TiO2-zeolite compound can adsorb organic molecules such as oleic acid and hematin, meanwhile, the rich silicon hydroxyl on the surface of the zeolite can form chemical anchoring with TiO2, so that the dispersion degree of the nanoparticles is increased to more than 85%, the inactivation of agglomeration is effectively inhibited, and the TiO2-zeolite compound can generate strong oxidizing active oxygen by excitation of ultraviolet rays, the active oxygen can degrade organic matter, and the residual compound after washing can continuously decompose residual organic matter of fabrics under natural light, so that the self-cleaning function is realized.

[0025] Meanwhile, the application also adds PCMX in the detergent, the PCMX can promote the absorption of ultraviolet rays by the detergent, the TiO2-zeolite compound can generate more active oxygen under excitation of ultraviolet rays, so that the degradation efficiency of the detergent on stubborn organic stains is improved, the problems of poor dispersion of TiO2 in the detergent and limited activation under light are solved, the stable release of the photocatalytic material in the washing process is realized, and the continuous and efficient cleaning effect is ensured, which can be applied to the scenes such as hospitals or industries that need a large amount of deep cleaning. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the application, the drawings needed to be used in the embodiments of the application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0027] Fig. 1 is the effect comparison diagram of sesame oil stained pieces after cleaning by the embodiment 1 and the comparative examples 1-4 of the application.

[0028] Fig. 2 is the effect comparison diagram of pig blood stained pieces after cleaning by the embodiment 1 and the comparative examples 1-4 of the application.

[0029] Fig. 3 is the effect comparison diagram of red dye stained pieces after cleaning by the embodiment 1 and the comparative examples 1-4 of the application. DETAILED DESCRIPTION

[0030] The technical solutions of the application will be further described below by combining the drawings and through specific embodiments.

[0031] In the drawings, only for example, the representation is a schematic diagram, not a physical diagram, and cannot be understood as a limitation of the patent; in order to better illustrate the embodiments of the present application, some components of the drawings may be omitted, enlarged or reduced, and do not represent the actual product size; 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 reference numerals in the drawings of the embodiments of the present application correspond to the same or similar components; in the description of the present application, it should be understood that if the terms "upper", "lower", "left", "right", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, only for the convenience of describing the present application and simplifying the description, and not to indicate or imply that the device or element referred to must have a particular orientation, structure and operation, therefore the positional relationship described in the drawings is only for example, and cannot be understood as a limitation of the patent, for those skilled in the art, the specific meaning of the above terms can be understood according to the specific circumstances.

[0033] In the description of the present application, unless otherwise explicitly specified and limited, if the term "connection" and the like appear to indicate the connection relationship between components, the term should be interpreted broadly, for example, it can be fixedly connected, or it can be detachably connected, or it can be integrated; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the internal communication of two components or the interaction relationship between two components. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0034] Embodiment 1:

[0035] The photocatalytic self-cleaning detergent of the present embodiment is prepared from the following raw materials by weight:

[0036]

[0037] When preparing the photocatalytic self-cleaning detergent, each raw material is added according to the above addition amount, including the following steps:

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

[0039] Tetrabutyl titanate and ethanol are mixed in a volume ratio of 1:3, under stirring at 200-300 rpm, ethanol is slowly added dropwise, after the dropwise addition of ethanol is completed, stirring is continued for 15-20 min, then deionized water is slowly added dropwise and the pH is adjusted to 3-4 with hydrochloric acid, the solution becomes turbid, and stirring is continued for 30-60 min to form a sol;

[0040] The rice husk ash was calcined at 600-700℃ for 2-3h to remove organic matter, and then treated with 1mL of hydrochloric acid at 80℃ for 2h, washed to neutral and dried; then the treated rice husk ash was mixed with metakaolin at a ratio of SiO2 / Al2O3=4, and water was added to prepare a slurry; the slurry was then transferred to a reaction kettle, and hydrothermal reaction was carried out at 120℃ for 6h, and finally the product was washed and dried to obtain a FAU type zeolite;

[0041] The FAU type zeolite was immersed in a sol, stirred for 6-8h, and then the FAU type zeolite was taken out and washed with deionized water, and dried at 80℃ for 12-15h; then calcined in a muffle furnace at a temperature rising rate of 2-3℃ / min to 450℃ for 2h to obtain a TiO2-zeolite composite.

[0042] (2) The TiO2-zeolite composite and polyvinylpyrrolidone were put into a ball mill, and the particle size was reduced to <10μm by grinding at a speed of 120r / min for 20min;

[0043] During the ball milling process, the mixing and grinding effect can be checked at any time, and the ball milling parameters can be adjusted according to the actual situation.

[0044] (3) The premixed material in the ball mill was transferred to a stirring container, and sodium dodecylbenzenesulfonate was added, and stirred at a speed of 2000r / min for 10-15min to make the sodium dodecylbenzenesulfonate fully mixed with the premixed material;

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

[0046] During the stirring process, the uniformity and fluidity of the system were observed, and timely adjustment was made if there was any abnormality.

[0047] (5) Protease and lipase were added in the stirring container, and stirred at a speed of 2000r / min for 30min to make the enzyme preparations fully contact and mix with other ingredients, forming a uniform mixture;

[0048] (6) p-Chloro-m-xylene phenol was added in the stirring container, and stirred at a speed of 2000r / min for 10min to form a uniform mixture;

[0049] (7) The pH value of the mixture was measured using a pH meter, and according to the measurement result, sodium carbonate was slowly added while continuously stirring, and the pH value of the system was maintained between 9-10, to obtain a photocatalytic self-cleaning detergent.

[0050] Comparative Example 1:

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

[0052]

[0053] The raw materials are added according to the above-mentioned adding amount when preparing the photocatalytic self-cleaning detergent, including the following steps:

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

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

[0056] Rice husk ash is calcined at 600-700°C for 2-3 h to remove organic matter, and then treated with 1 mL of hydrochloric acid at 80°C for 2 h. After washing to neutral, it is dried. Then the treated rice husk ash is mixed with metakaolin at a ratio of SiO2 / Al2O3=4, and water is added to prepare a slurry. The slurry is then transferred to a reaction kettle and hydrothermally reacted at 120°C for 6 h. Finally, the product is washed and dried to obtain FAU-type zeolite;

[0057] The FAU-type zeolite is immersed in the sol and stirred for 6-8 h. Then the FAU-type zeolite is taken out and washed with deionized water, and dried at 80°C for 12-15 h. Then it is calcined in a muffle furnace at a temperature increasing rate of 2-3°C / min to 450°C for 2 h to obtain a TiO2-zeolite composite.

[0058] (2) The TiO2-zeolite composite and polyvinylpyrrolidone are 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 mixing and grinding effect can be checked in time, and the ball milling parameters can be adjusted according to the actual situation.

[0060] (3) The premixed material in the ball mill is transferred to a stirring container, and sodium dodecylbenzenesulfonate is added. The stirring speed is 2000 r / min, and the stirring time is 10-15 min, so that the sodium dodecylbenzenesulfonate is fully mixed with the premixed material;

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

[0062] During the stirring process, the uniformity and fluidity of the system should be observed, and timely adjustment should be made if there is any abnormality.

[0063] (5) Add protease and lipase into the stirring container, stir at the speed of 2000 r / min for 30 min, so that the enzyme preparation is in full contact and mixing with other ingredients to form a uniform mixture;

[0064] (6) Measure the pH value of the mixture using a pH meter, slowly add sodium carbonate according to the measurement results and continuously stir, maintain the pH value of the system between 9-10, and prepare a photocatalytic self-cleaning detergent without PCMX.

[0065] Comparative Example 2:

[0066] The detergent of the present example is prepared by reacting the following raw materials by weight:

[0067]

[0068]

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

[0070] (1) Put polyvinylpyrrolidone into a ball mill, grind at the speed of 120 r / min for 20 min, and reduce the particle size to <10 μm;

[0071] During the ball milling process, the milling effect can be checked in time, and the ball milling parameters can be adjusted according to the actual situation.

[0072] (2) Transfer the material in the ball mill to a stirring container, and add sodium dodecylbenzenesulfonate, stir at the speed of 2000 r / min for 10-15 min, so that the sodium dodecylbenzenesulfonate is fully mixed with the material;

[0073] (3) Add sodium citrate and sodium silicate into the stirring container in turn, stir at the speed of 2000 r / min for 10-15 min, so that they are uniformly dispersed in the system;

[0074] During the stirring process, the uniformity and fluidity of the system should be observed, and adjusted in time if there is any abnormality.

[0075] (4) Add protease and lipase into the stirring container, stir at the speed of 2000 r / min for 30 min, so that the enzyme preparation is in full contact and mixing with other ingredients to form a uniform mixture;

[0076] (5) Add p-chloro-m-xylene phenol into the stirring container, stir at the speed of 2000 r / min for 10 min, and form a uniform mixture;

[0077] (6) using a pH meter to measure the pH value of the mixture, slowly adding sodium carbonate according to the measurement results and continuously stirring, maintaining the pH value of the system between 9-10, and preparing a detergent without TiO2-zeolite composite.

[0078] Comparative Example 3:

[0079] The detergent of the present example is prepared by reacting the following raw materials by weight:

[0080]

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

[0082] (1) Put the polyvinylpyrrolidone into 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 grinding effect can be checked in time, and the ball milling parameters can be adjusted according to the actual situation.

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

[0085] (3) Add sodium citrate and sodium silicate in the stirring container in turn, and stir at a speed of 2000 r / min for 10-15 min to make them uniformly dispersed in the system;

[0086] During stirring, pay attention to the uniformity and fluidity of the system, and adjust in time if there is any abnormality.

[0087] (4) Add protease and lipase in the stirring container, stir at a speed of 2000 r / min for 30 min to make the enzyme preparations fully contact and mix with other ingredients, forming a uniform mixture;

[0088] (5) using a pH meter to measure the pH value of the mixture, slowly adding sodium carbonate according to the measurement results and continuously stirring, maintaining the pH value of the system between 9-10, and preparing a detergent without TiO2-zeolite composite and PCMX.

[0089] Comparative Example 4:

[0090] The detergent of the present example is a standard detergent prepared according to Appendix B of the national standard GB / T 13174-2021 "Detergent for clothing Stain removal and cyclic washing performance test".

[0091] Effect of the examples and comparative examples:

[0092] 1. Stain removal experiment:

[0093] 1.1 Preparation of stained cloth:

[0094] 1.1.1 Cut the standard white cotton cloth into 6cm*6cm square cloth pieces and put them into the washing machine for washing according to the standard program (the total washing time is 51 min, including 1 main washing of 13 min, 2 rinsing, and 1 dehydration of 5 min).

[0095] 1.1.2 After washing, take out the cloth pieces and wash them in a suitable container with 60℃ deionized water for 30 min.

[0096] 1.1.3 After the second washing, take out the cloth pieces, spin dry, and iron them flat with an electric iron, ready for use.

[0097] 1.1.4 Dip the cloth pieces prepared in 1.1.3 in the stain solution (the stain solution is divided into three groups: oil, blood, and dye, where the oil represents sesame oil, the blood represents pig blood, and the dye represents red dye), and if the cloth pieces are not fully immersed, apply some pressure on top of the cloth pieces. After 20 min, take them out and dry them at room temperature, ready for use. If the cloth pieces have wrinkles, iron them flat with an electric iron.

[0098] 1.2 Test steps

[0099] 1.2.1 Take 4 pieces of blank cloth prepared in 1.1.3 as the experimental group, and take 4 pieces of blank cloth as the control group. According to the method of standard GB / T 13174-2021, measure the whiteness value of the diagonal line of each blank cloth on both sides. Each group gets 16 data, which is recorded as F0.

[0100] 1.2.2 Dip the cloth pieces with measured initial whiteness value in 1.2.1 according to the steps of 1.1.4 to make experimental stained cloth pieces. Measure the whiteness value of the cloth pieces again, which is recorded as F1.

[0101] 1.2.3 Perform washing test in a vertical stain remover. Turn on the UV ultraviolet lamp during the whole process. Before measurement, number and fix the stirring impeller, working tank, and stain remover bath one by one to form a "working unit". During the test, use 250mg / kg hard water (preheated to about 30℃ before use) to prepare the detergent of Example 1 and Comparative Examples 1-4 into a certain concentration (if not specified, the solution concentration is 0.2%) of test solution 1L, and pour it into the corresponding stain remover bath. Put the bath into the corresponding position and install the stirring impeller. Adjust the instrument to keep the washing test temperature at 30℃±1℃, and prepare for measurement.

[0102] 1.2.4 Put the stained cloth pieces of 1.2.2 into the bath, start stirring, and keep the stirring speed at 120r / min. Stop after 20 min of washing.

[0103] 1.2.5 Remove the test piece from the cleaning bath and place it in the inner tub of the rinser. Spin-dry for 15 seconds (inner tub speed approximately 1800 rpm) and drain. Then pour 1500 mL of tap water into the rinser, replace the lid, and rinse the test piece for 30 seconds at a uniform speed, alternating between 5 clockwise and 5 counterclockwise rotations. During this time, the inner tub should be fully rotated, but care should be taken to avoid overflowing the rinse water due to excessive rotation. Drain the rinse water and manually spin-dry the test piece for 15 seconds. Add 1500 mL of tap water again and repeat the second rinse and spin-drying process. Repeat this process four times in total. After the final rinse and spin-drying, remove the test piece and place it on an enamel dish to air dry at room temperature. Measure the whiteness F2 (experimental results can be referenced). Fig. 1 to Fig. 3 ).

[0104] 2. Detergent power test data

[0105] 2.1 Calculation of stain removal rate:

[0106]

[0107] In the formula, i represents the i-th type of soiled cloth test piece; F 0i -F 1i F represents the whiteness value of the i-th type of soiled cloth sample stained with the experimental stain; 2i -F 1i The result is the whiteness value of the i-th type of soiled cloth sample after washing away the experimental stain; the result is retained to one decimal place.

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

[0109]

[0110] In the formula The stain removal rate of the test samples in the experimental group; The standard detergent was used as the control group to measure the stain removal rate in the experiment; the results are rounded to one decimal place.

[0111] 2.3 Experimental Data

[0112] 2.3.1 Experimental data of standard detergents

[0113] Table 1: Changes in whiteness values ​​of experimental fabric samples treated with the standard detergent in Comparative Example 4

[0114]

[0115]

[0116] 2.3.2 Experimental data of Example 1

[0117] Table 2: Change of whiteness value of experimental swatches of photocatalytic self-cleaning detergent of Example 1

[0118]

[0119] Table 3: Ratio of experimental stain removal of Example 1

[0120]

[0121]

[0122] As can be seen from Table 3, in the stain removal experiment, the photocatalytic self-cleaning detergent of Example 1 has a significantly higher removal rate of different organic stains such as oil, blood, and dye than the standard detergent of Comparative Example 4, thus proving that the photocatalytic self-cleaning detergent of the present example can effectively improve the stain removal effect.

[0123] 2.3.3 Experimental data of Comparative Example 1

[0124] Table 4: Change of whiteness value of experimental swatches of detergent without PCMX of Comparative Example 1

[0125]

[0126] Table 5: Ratio of experimental stain removal of Comparative Example 1

[0127] Name of stained cloth Removal ratio ratio (P i )]]> Sesame oil 1.9 Pig blood 2.2 Red dye 2.2

[0128] As can be seen from Table 3 and Table 5, in the stain removal experiment, the photocatalytic self-cleaning detergent of Example 1 has a significantly higher ratio of removal rate of different organic stains such as oil, blood, and dye than the detergent without PCMX of Comparative Example 1, thus proving that the PCMX raw material plays an important role in the detergent, which can help the detergent improve the stain removal effect.

[0129] 2.3.4 Experimental data of Comparative Example 2

[0130] Table 6: Change of whiteness value of experimental swatches of detergent without TiO2-zeolite composite of Comparative Example 2

[0131]

[0132] Table 7: Ratio of experimental stain removal of Comparative Example 2

[0133] Name of stained cloth Removal ratio ratio (P i )]]> Sesame oil 1.3 Pig blood 1.3 Red dye 1.3

[0134] As can be seen from Table 3 and Table 7, the photocatalytic self-cleaning detergent containing the TiO2-zeolite composite of Example 1 and the detergent not containing the TiO2-zeolite composite of Comparative Example 2 have the removal rate ratio of different organic stains such as oil, blood, and dye in the stain removal experiment, and the removal rate ratio of the detergent of Example 1 is significantly higher than that of Comparative Example 2, thereby proving that the TiO2-zeolite composite plays an important role in the detergent, and the key is that the TiO2-zeolite composite prepared from rice husk ash and metakaolin has a unique three-dimensional porous structure to adsorb organic molecules such as oleic acid and hematin, and the abundant silicon hydroxyl groups on the surface of the zeolite form chemical anchoring with TiO2, which can improve the dispersion degree of nanoparticles to more than 85%, effectively inhibit the agglomeration and inactivation, and the TiO2-zeolite composite can generate active oxygen with strong oxidation by ultraviolet excitation, which can degrade organic matter, and the residual composite after washing can continuously decompose the residual organic matter of the fabric under natural light, thereby realizing the self-cleaning function.

[0135] 2.3.5 Experimental data of Comparative Example 3

[0136] Table 8: Change table of whiteness value of experimental cloth of the detergent of Comparative Example 3 not containing the TiO2-zeolite composite and PCMX

[0137]

[0138]

[0139] Table 9: Experimental stain removal rate ratio table of Comparative Example 3

[0140] Name of stained cloth Removal ratio ratio (P i )]]> Sesame oil 1.0 Pig blood 1.3 Red dye 1.0

[0141] As can be seen from Table 3, Table 5, Table 7, and Table 9, the photocatalytic self-cleaning detergent containing the TiO2-zeolite composite and PCMX of Example 1, the detergent not containing PCMX of Comparative Example 1, and the detergent not containing the TiO2-zeolite composite of Comparative Example 2 have the removal rate ratio of different organic stains such as oil, blood, and dye in the stain removal experiment, and the removal rate ratio of the detergent of Example 1, Comparative Example 1-2 is significantly higher than that of Comparative Example 3, thereby proving that the addition of the TiO2-zeolite composite and PCMX raw materials in the detergent can effectively improve the stain removal effect.

[0142] 3. Ultraviolet absorption experiment

[0143] 3.1 Solution preparation: 2 g of the detergent of Example 1 and Comparative Example 1 was accurately weighed into two 1 L volumetric flasks, respectively, and an appropriate amount of tap water was added, and mixed thoroughly, and then diluted to the calibration line.

[0144] 3.2 Take two clean quartz cuvettes, add an appropriate amount of the prepared solution, and place them in the ultraviolet spectrophotometer. Set the ultraviolet region (200-400nm), and scan the spectra of the two solutions to 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 Analysis of experimental results:

[0150] As can be seen from Table 10, the photocatalytic self-cleaning detergent containing PCMX in Example 1 has a significantly higher absorbance than the photocatalytic self-cleaning detergent without PCMX in Comparative Example 1 in the ultraviolet region of 200-400nm, which proves that the addition of PCMX in Example 1 not only plays an antibacterial role, but also significantly enhances the absorption of ultraviolet light by the detergent;

[0151] Therefore, it can be seen that PCMX can improve the detergency of the detergent, mainly because PCMX promotes the absorption of ultraviolet light by the detergent, and TiO2-zeolite composite generates more active oxygen under the excitation of ultraviolet light, thereby improving the degradation efficiency of the detergent on stubborn organic stains, solving the problems of poor dispersibility of TiO2 in the detergent and limited photoactivation, realizing the stable release of photocatalytic materials in the washing process, and ensuring sustained and efficient cleaning effect, which can be applied to hospital or industrial scenes that require a large amount of deep cleaning.

[0152] It should be noted that the above specific embodiments are only the preferred embodiments of the present application and the technical principles applied. Those skilled in the art should understand that various modifications, equivalent replacements, changes, etc. can be made to the present application. However, as long as these changes do not deviate from the spirit of the present application, they should be within the protection scope of the present application. In addition, some terms used in the specification and claims of the present application are not limited, but are only used for convenience of description.

Claims

1. A photocatalytic self-cleaning detergent, characterized by, By weight parts, including the following components: TiO2-zeolite complex 5-10 parts; p-chloro-m-dichlorophenol 2-3 parts; Sodium citrate 5-8 parts; Sodium silicate 3-5 parts; Polyvinylpyrrolidone 1-2 parts; Surfactant 20-30 parts; Enzyme preparation 0.2-1 part; pH regulator 2-3 parts; Water 50-70 parts; The surfactant is sodium dodecyl benzene sulfonate, and the pH regulator is sodium carbonate; The preparation method of the TiO2-zeolite complex includes the following steps: Tetrabutyl titanate is mixed with ethanol at a volume ratio of 1:3, and under stirring at 200-300 rpm, deionized water is slowly added dropwise, and hydrochloric acid is used to adjust the pH to 3-4. After the solution becomes turbid, continue stirring for 30-60 min to form a sol; Rice husk ash is calcined at 600-700°C for 2-3h to remove organic matter, then treated with 1mL hydrochloric acid at 80°C for 2h, washed to neutral and dried; then the treated rice husk ash is mixed with metakaolin at a ratio of SiO2 / Al2O3=4, and water is added to make a slurry; then the slurry is transferred to a reaction kettle, and hydrothermal reaction is carried out at 120°C for 6h, and finally the product is washed and dried to obtain FAU type zeolite; The FAU type zeolite is immersed in the sol and stirred for 6-8h, then the FAU type zeolite is taken out and washed with deionized water, and dried at 80°C for 12-15h; then calcined in a muffle furnace at a heating rate of 2-3°C / min to 450°C for 2h to obtain the TiO2-zeolite complex.

2. The photocatalytic self-cleaning detergent according to claim 1, characterized in that, By weight parts, including the following components: TiO2-zeolite complex 8 parts; p-chloro-m-dichlorophenol 2.5 parts; Sodium citrate 5.5 parts; Sodium silicate 4.5 parts; Polyvinylpyrrolidone 1.5 parts; Surfactant 20 parts; Enzyme preparation 0.5 parts; pH regulator 2.5 parts; Water 55 parts. 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. A method for the preparation of a photocatalytic self-cleaning detergent according to any one of claims 1 to 3, characterized in that, Including the following steps: S1, preparing TiO2-zeolite complex; S2, putting the TiO2-zeolite complex and polyvinylpyrrolidone into a ball mill and grinding for 20 min to reduce the particle size to <10μm; S3, transferring the premixed material in the ball mill to a stirring container and adding surfactant, stirring for 10-15 min to fully mix the surfactant with the premixed material; S4, adding sodium citrate and sodium silicate in the stirring container in turn, stirring for 10-15 min to make them uniformly dispersed in the system; S5, adding enzyme preparation in the stirring container, stirring for 30 min; S6, adding p-chloro-m-dichlorophenol in the stirring container, stirring for 10 min to form a uniform mixture; S7, measuring the pH value of the mixture, slowly adding the pH regulator according to the measurement results and continuously stirring to maintain the pH value of the system between 9-10 to prepare the photocatalytic self-cleaning detergent.

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