Modified titanium dioxide odor-removing product and manufacturing method thereof

Abstract

The invention discloses a modified titanium dioxide odor-removing product applied to the field of environmental protection and a manufacturing method thereof. The product forms comprise powder, paste and spray, a light inducer and a light absorber as modified materials, the modified materials are dissolved in a solvent to form a modified impregnation liquid, the modified materials are attached to the surfaces or cavities of titanium dioxide particles through impregnation and grinding, and ultraviolet light is transmitted to the shady surface of the particles under the combined action of the two agents, so that the shady surface has a'photocatalyst 'catalytic effect. Materials used for a powdery product mainly comprise titanium dioxide particles, a light inducer, a light absorbent, a solvent and the like, an adhesive, a cross-linking agent and the like are added to a pasty material, and yttrium oxide, antibacterial perfume and the like are added to a spray product. The powder can be used for deodorizing sewage, the paste can be used for deodorizing outdoor dirt and large space after being diluted, and the spray is suitable for deodorizing living rooms.

Description

Technical Field

[0001] The present invention is applied to the field of environmental protection and relates to titanium dioxide purification materials, specifically a modified nano titanium dioxide deodorizing product and a manufacturing method thereof, which can be used for deodorizing fluids and removing odors emitted into the air. Background Art

[0002] Titanium dioxide (TiO2), capable of capturing photons and achieving charge separation, is the most commonly used photocatalytic material. This type of inorganic semiconductor photocatalyst achieves its photocatalytic degradation function by generating electrons and holes through light excitation, which then undergo reduction and oxidation reactions with species adsorbed on the catalyst surface. This effectively degrades toxic and harmful gases in the air and kills a variety of bacteria. It also removes formaldehyde, deodorizes, resists pollution, and purifies the air. Ultraviolet light has a wavelength of 100-400 nm, while visible light has a wavelength of 400-800 nm. Titanium dioxide photocatalytic particles are nanoscale spherical structures with a diameter of 1-10 nm. Only the hemisphere facing the light exerts a "photocatalytic" catalytic effect, while the hemisphere facing away from the light, lacking any catalytic activity and remaining in a semi-dormant state, indicates that nano-titanium dioxide particles still have potential for photocatalysis. Therefore, modifying nano-titanium dioxide to maximize its adsorption and degradation capabilities has become a major research focus for purification materials.

[0003] Numerous patent applications exist for methods and materials for modifying titanium dioxide. For example, CN1583252A discloses a method for preparing a visible-light-responsive titanium dioxide photocatalyst for indoor air purifiers. The modifying metal is a combination of the rare metals lanthanum and cerium and transition metal oxides such as manganese, iron, cobalt, nickel, and copper, forming a metal oxide / titanium dioxide heterojunction to modify the titanium dioxide. CN112007628A discloses an air purification material and its preparation method, comprising a stacked ceramic foam loaded with graphene-modified titanium dioxide; the graphene-modified titanium dioxide loading is 1% to 20%. By loading the ceramic foam with graphene-modified titanium dioxide, the material achieves air purification. Graphene's excellent electrical conductivity significantly reduces the recombination rate of photogenerated electrons, thereby significantly improving catalytic activity and light energy utilization. CN101391210B discloses a method for preparing a laser-modified titanium dioxide photocatalyst, including: 1) surface treatment of a high-strength, highly elastic, porous polyester fiber mesh; 2) loading the titanium dioxide photocatalyst; and 3) modification in a textile laser processor to produce a laser-modified titanium dioxide film. Under weak alkaline conditions, isopropyl titanate and isobutyl alcohol are used as raw materials, and a sol-gel coating method is used to form a film on the fiber mesh surface, which is then modified in a textile laser processor. CN102441372A provides a method for improving the photocatalytic performance of nano-titanium dioxide. Nano-TiO2 is doped and modified by hydrolyzing 4-7% titanium sulfate with 0.1-0.4% tetrabutylammonium hydroxide to produce TiO2-C, which exhibits photocatalytic response across a wider range of light wavelengths. Furthermore, activated carbon is used as a carrier for the nano-TiO2, leveraging its adsorption properties to rapidly enrich various pollutants. CN108906017A discloses a method for preparing a photocatalytic material for air purification, comprising: (1) magnetic stirring and hydrolysis reaction at 120-180°C; (2) heat treatment at 700-1000°C to prepare modified titanium dioxide; (3) preparing a titanium dioxide composite photocatalyst suspension using the modified titanium dioxide as a raw material; (4) preparing a hollow carbon fiber carrier; (5) immersing the hollow carbon fiber carrier in the titanium dioxide composite photocatalyst suspension, pulling it out and drying it at 90-110°C; further immersing the dried hollow carbon fiber carrier in the titanium dioxide composite photocatalyst suspension, pulling it out and drying it again to obtain a photocatalytic material for air purification. CN111318275B discloses a photocatalyst suitable for indoor air purification in dim light, comprising modified titanium dioxide particles and quantum dots, wherein the modified titanium dioxide particles are titanium dioxide particles grafted with alkenyl cage-type silsesquioxane.After the alkenyl cage silsesquioxane-grafted titanium dioxide particles are physically blended with quantum dots and then doped into the photocatalyst formula, a good synergistic effect can be achieved, which can effectively improve the efficiency of the titanium dioxide particles in the photocatalyst in absorbing solar energy. Even in indoor environments with insufficient light, the photocatalyst can have good sterilization, formaldehyde removal and mildew prevention effects.

[0004] It can be seen that in the above patent applications, the modification methods of titanium dioxide include doping, impregnation, laser, etc., and the modification materials include modified metals, metal oxides, graphene, activated carbon, etc., none of which solves the problem of improving the catalytic ability of the backlight side of titanium dioxide particles. Summary of the Invention

[0005] The technical problem solved by this invention is to provide a modified titanium dioxide deodorizing product and manufacturing method. Using a light inducer and a light absorber as modifying materials, the modified particles are impregnated and coated. The combined action of these two agents directs ultraviolet light to the backlit side of the titanium dioxide particles, improving their photosensitivity and chemical properties, tapping into the potential of photocatalysis and enhancing the degradation of odorous or harmful gases. The addition of an antibacterial fragrance enhances its bactericidal and antibacterial properties.

[0006] The product forms of the present invention include powder, paste and spray. Photoinducers and light absorbers are used as modified materials, which are dissolved in a solvent to prepare a modified impregnation liquid. The modified materials are attached to the surface or cavity of titanium dioxide particles by an impregnation method. The combined action of the photoinducers and light absorbers transmits ultraviolet light to the backlit side of the titanium dioxide particles, so that the backlit side of TiO2 is exposed to ultraviolet light, which has a "photocatalytic" catalytic effect and achieves the purpose of degradation, sterilization and antibacterial. The materials used in the powdered deodorizing product of the present invention mainly include titanium dioxide particles, photoinducers, light absorbers, solvents, etc. The materials used in the paste deodorizing product are based on these materials and have added adhesives, cross-linking agents, etc. The spray deodorizing product is based on the materials used in the paste product and has added yttrium oxide, antibacterial fragrances, etc.

[0007] Photoinitiators are organic compounds that can induce ultraviolet light. Under natural sunlight, their emission spectrum extends over a wider range. They enable titanium dioxide nanoparticles to absorb specific wavelengths of energy in the ultraviolet or visible region, generating free radicals or ions, which in turn initiate polymerization and crosslinking of the monomers to form a cured compound. Upon exposure to light, some monomers absorb photons and form excited states. These excited active molecules undergo homolytic cleavage to generate free radicals, which in turn initiate polymerization and form polymers. Photoinitiators typically possess the following properties: 1) Photosensitivity. Photoinitiators absorb specific wavelengths of light, broadening the wavelength range of the excitation light and increasing the efficiency of nano-TiO2 in utilizing natural sunlight. Photoexcitation results in a high-energy or excited state, enhancing the photosensitivity of TiO2. 2) High chemical activity. The excited state of the photoinitiator can react with other molecules, generating free radicals or ions and initiating chemical reactions. 3) Controllability. The activity of the photoinitiator can be manipulated by varying the intensity and wavelength of the light source. The photoinducers used in this application include benzoin isopropyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 4-methylbenzophenone, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, phenyl salicylate, octyl methoxycinnamate, 2-hydroxy-2-methylphenylpropane-1-one, etc.

[0008] Light absorbers are UV absorbers and light stabilizers with exceptionally strong UV absorption capabilities. They can absorb the ultraviolet portion of sunlight and fluorescent light sources without changing themselves. Based on their chemical structure, they can be categorized into salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and hindered amines. Light absorbers used in this application include benzophenone, methyl o-benzoylbenzoate, 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (UV-320), and benzophenone.

[0009] When nano-titanium dioxide is irradiated by light, its electrons are excited from the valence band to the conduction band, generating O2 on the surface of titanium dioxide. - Titanium dioxide and OH·, both of which have redox properties, can decompose organic matter, oxidize chemicals, and kill bacteria, thereby degrading odor molecules and sterilizing and purifying the air. Titanium dioxide also absorbs ultraviolet light, forming excited electrons and holes, which break DNA molecules in bacteria, thereby achieving a sterilizing effect. Furthermore, titanium dioxide's absorption of ultraviolet light also produces hydroxyl radicals, which can kill most bacteria and viruses and have a good broad-spectrum activity. Titanium dioxide also has the effect of inhibiting cellular metabolism in some bacteria. Bacteria produce harmful substances such as hydrogen peroxide and superoxide ions as they produce metabolic products. Titanium dioxide can inhibit the production of these harmful substances, thereby inhibiting bacterial cell metabolism.

[0010] On the light-facing side, the photoinducer enhances the light intensity on TiO2, increasing its photosensitivity and high chemical activity. Under natural light conditions, the photoinducer intensifies its luminescence, and the surrounding light absorbers absorb light, causing the photoinducers around the light absorbers to emit light. The combined action of the two agents, the ultraviolet light absorption and the induction process to the surrounding area, transmits ultraviolet light to the backlit side, allowing the backlit side of the TiO2 to receive ultraviolet light, which has a "photocatalytic" catalytic effect, awakening its semi-dormant state and achieving the purpose of degradation, bactericidal and antibacterial. TiO2 can be effectively excited within the ultraviolet wavelength range of 100-400nm. Within this range, the wider the ultraviolet wavelength overlap between the photoabsorber and the photoinducer, the more complete the excitation of the backlit side of TiO2, and the better the "photocatalytic" catalytic effect of the backlit side. The combination of photoinducer and light absorber should be guided by the wavelength overlap range of ultraviolet light, and a combination of two agents with a wide wavelength overlap range should be used. To increase the UV wavelength range, a combination of two or more photoinducers and / or two or more light absorbers can be used. A 1:1 molar ratio of the two agents achieves the best combined modification and triggering effect. When using two or more photoinducers or light absorbers, calculate the molar ratio as if they were a single unit. Typically, the molar ratio is controlled to be 1:0.8-1.2.

[0011] This invention uses an impregnation method to modify titanium dioxide, attaching modifying materials (photoinducers and light absorbers) to the surface or cavities of titanium dioxide particles to produce modified nano-titanium dioxide. Specifically, the modifying material, acting as a solute, is dissolved in a solvent to form a modified impregnation solution. The titanium dioxide particles are then dispersed and immersed in the modified impregnation solution, where the modifying material infiltrates the surface of the titanium dioxide particles and penetrates into their cavities. After drying, the solvent evaporates or volatilizes, and the solute atoms of the modifying material adhere to the surface and cavities of the titanium dioxide particles in a bonded network structure, coating the titanium dioxide particles. This imparts a catalytic effect to the entire spherical surface of the titanium dioxide, increasing the generation of electron-hole pairs on the backlit side of the sphere, enabling rapid electron absorption and excitation, and thus doubling the titanium dioxide's pollutant degradation rate. For optimal modification, the weight ratio of modifying material to titanium dioxide particles should be no less than 1:7.

[0012] The solvent used in the modified impregnation solution is a water-soluble organic solvent, such as methanol, ethanol, acetone, glycerol (propylene glycol), or a combination of two or more. These solvents can dissolve the solute and chemically disperse the titanium dioxide particles. They are also miscible with water and have low surface tension, facilitating impregnation. These organic solvents are easily volatile, facilitating powder drying or post-spray drying. If necessary, water can partially replace the solvent to reduce solvent costs or prevent fire hazards caused by organic solvents. However, a crosslinking agent must be added to prevent organic precipitation. This invention primarily uses ethanol as the solvent due to its suitable volatility. Methanol is toxic and should be used with caution; acetone is highly volatile and wasteful. To achieve a single impregnation, the weight ratio of the modified material to the titanium dioxide particles must meet the required value, and the concentration of the modified impregnation solution should be between 10% and 35%.

[0013] Paste products need to be diluted with water before use. This serves as a fluid and carrier for spraying and adhering the modified titanium dioxide particles to walls or roofs in a short period of time, requiring the addition of an adhesive. Water-soluble adhesives, such as water glass, silica sol, and 107 glue, are ideal. First, their water solubility facilitates cleaning; titanium dioxide particles sprayed on furniture surfaces can be removed with a damp cloth. Second, their strong adhesion allows the modified titanium dioxide particles to adhere to walls or roofs for extended periods, effectively removing odors. Third, they are environmentally friendly and odorless. The weight ratio of adhesive to titanium dioxide particles should be no less than 1:20.

[0014] Photoinducers and photoabsorbers are generally insoluble in water. To prevent the precipitation of these solutes during dilution of the paste product with water, a crosslinker must be added to the spray. The function of a crosslinker is to form an "oil-in-water" or "water-in-oil" emulsion, connecting inorganic and organic molecules and thus preventing the precipitation of organic matter from the water. Crosslinkers are Tween surfactants and coupling agents. Tween surfactants are readily soluble in water and ethanol and have a strong emulsifying effect. Tween 80 was primarily used in the experiments. Silane coupling agents or titanate coupling agents are used as coupling agents. The silane alkoxy groups of silane coupling agents are reactive with inorganic substances, while the organic functional groups are reactive or compatible with organic substances, forming a bonding layer between the organic matrix, the silane coupling agent, and the inorganic matrix. The molecular formula of a titanate coupling agent is (RO)m Ti(OX-RY)n. Its molecular structure dictates its multiple functions. (RO)m forms a monolayer of the coupling agent through the R group with the inorganic filler, acting as a chemical coupling agent. Water and free protons (H+) at the filler interface serve as active reaction sites. (O-) can undergo various esterification reactions, allowing the titanate to crosslink with polymers and also undergo esterification with hydroxyl groups in epoxy resins. X is the atomic group that connects the titanium oxide bond and determines the properties of the titanate. R is the long chain portion of the titanate molecule, primarily ensuring entanglement and compatibility with polymer molecules. Y is the functional group that crosslinks the titanate. n reflects the number of functional groups present in the titanate molecule. The crosslinker dosage ranges from 0.1% to 3% by weight of the adhesive.

[0015] Yttrium oxide is insoluble in water and alkali, but soluble in acid and alcohol. The radius of yttrium ion (0.089 nm) is similar to that of titanium ion (0.068 nm), which makes Y 3+ It is easier to enter the TiO2 lattice gap, more evenly distributed in TiO2, and Y 3+ The energy level is close to the TiO2 conduction band, which can reduce the recombination of electrons and holes. 3+ Doping modification makes nano-TiO2 enhance its "photocatalytic" effect.

[0016] Antibacterial spices include storax or borneol. Styrax is an orifice-opening herb that dissolves in ethanol. It is a semi-fluid, thick liquid ranging from yellowish-white to grayish-brown, translucent, and viscous, flowing continuously when picked up. It is heavy and sinks in water. It has a fragrant aroma and a slightly bitter, spicy, and fragrant taste. Soak it in clean water and store it in a cool place to prevent the loss of its aroma. It also has a weak antibacterial effect and is mainly used to open the orifices, dispel filth, relieve depression, and eliminate phlegm. It is used to treat sudden fainting, phlegm-congested qi syncope, epilepsy, febrile malaria, and sudden heart and abdominal pain. Borneol (borneol, borneol tablets) is mainly composed of crystals obtained from the resin and volatile oil of borneol, and is a nearly pure dextrorotatory borneol. Borneol is a colorless, transparent or white, translucent, flaky, crisp crystal with a light fragrance and a pungent, cool taste. It is volatile and easily sublimates. It is easily soluble in ethanol, gasoline, or ether, but almost insoluble in water. It has antibacterial, antimicrobial, and anti-inflammatory effects, and can significantly inhibit egg white-induced plantar swelling in rats, inhibiting inflammatory processes such as fluid exudation and tissue edema. In addition, styrax or borneol have a high photosensitivity reaction and can assist the photosensitization of light inducers and light absorbers.

[0017] Yttrium oxide and an antibacterial fragrance act as solutes and are dissolved in a water-soluble organic solvent. These solutes penetrate the surface and cavities of titanium dioxide particles. After evaporation or drying of the solvent, the yttrium oxide forms ion doping, enhancing the catalytic activity of the titanium dioxide particles. The yttrium oxide should account for no more than 40% of the titanium dioxide particles by weight. A photoinitiator, a light absorber, and an antibacterial fragrance are attached to the surface and cavities of the titanium dioxide particles. The amount of the antibacterial fragrance added should be 15% to 50% of the weight of the two doses, with the total weight of the photoinitiator, light absorber, and antibacterial fragrance to the titanium dioxide particles being no less than 1:5. In addition to the yttrium oxide ion doping modification, the modified materials, photoinitiator and light absorber, are added to transmit ultraviolet light to the backlit side of the particles, activating the catalytic activity of the titanium dioxide on this backlit side. This increases the photosensitivity and chemical resistance of the titanium dioxide particles, enhancing their ability to degrade odors or harmful gases. The titanium dioxide and antibacterial fragrance act as bactericides and antibacterial agents, strengthening their bactericidal and antibacterial properties. Antibacterial fragrances emit a fragrant aroma that helps inhibit and fight bacteria, clear the body's pores, and dispel filth. Under the influence of ultraviolet light, the antibacterial fragrance leverages the photosensitivity of borneol and styrax, creating a synergistic effect with photoinducers and absorbers, emitting an antibacterial fragrance that works in conjunction with titanium dioxide to achieve antibacterial, sterilization, degradation, and deodorization. For spray products, water is used as an inexpensive diluent. This dilution water is added to the milled liquid to improve the fluidity of the particles and ensure uniform spraying. The crosslinker and binder in the spray comprise 0.2% to 0.8% and 0.2% to 2% of the water weight, respectively.

[0018] The preparation method of modified titanium dioxide deodorizing powder includes the following steps: 1) preparing titanium dioxide microparticles: preparing titanium dioxide particles by a sol-gel method or purchasing titanium dioxide particles, and crushing them into microparticles; or purchasing titanium dioxide microparticles; 2) preparing a modified impregnation liquid: stirring and dissolving the modified material in a water-soluble organic solvent, or in a mixture of a water-soluble organic solvent and water, to prepare a modified impregnation liquid; 3) preparing modified titanium dioxide powder: mixing the titanium dioxide microparticles with the modified impregnation liquid, stirring and impregnating, grinding and impregnating, filtering and drying to obtain modified titanium dioxide powder; 4) making modified titanium dioxide deodorizing powder: crushing the modified titanium dioxide powder to obtain modified titanium dioxide deodorizing powder.

[0019] The preparation method of a modified titanium dioxide deodorizing paste comprises the following steps: 1) preparing titanium dioxide microparticles (as described above); 2) preparing a modified impregnation solution (as described above); 3) impregnating the mixture into an impregnation paste (as described above); mixing the titanium dioxide microparticles with the modified impregnation solution, stirring, impregnating, and grinding the mixture to form an impregnation paste; and 4) preparing the modified titanium dioxide deodorizing paste (as described above); adding a binder and a crosslinking agent to the impregnation paste, stirring, and grinding the mixture to obtain the modified titanium dioxide deodorizing paste. Alternatively, the binder and crosslinking agent may be added to water and stirred to form a binder solution. The modified titanium dioxide deodorizing powder may then be added to the binder solution, stirred, and ground to obtain the modified titanium dioxide deodorizing paste.

[0020] The preparation method of a modified titanium dioxide deodorizing spray comprises the following steps: 1) preparing titanium dioxide microparticles and yttrium oxide microparticles; 2) preparing a modified impregnation solution: stirring and dissolving a photoinducer, a photoabsorber and an antibacterial fragrance in a water-soluble organic solvent, or a mixture of a water-soluble organic solvent and water, to prepare a modified impregnation solution; 3) preparing an impregnating titanium dioxide liquid: adding titanium dioxide microparticles and yttrium oxide microparticles to the modified impregnation solution and stirring; after stirring and impregnating and grinding, the ethanol solution in which the photoinducer, photoabsorber, antibacterial fragrance and yttrium oxide are dissolved gradually penetrates into the surface and cavities of the microparticles to form an impregnating titanium dioxide liquid; 4) preparing a colloidal solution: adding a water-soluble adhesive and a cross-linking agent into water, stirring evenly, and dissolving them to form a colloidal solution; 5) making a modified titanium dioxide deodorizing spray: mixing the impregnating titanium dioxide liquid with the colloidal solution, stirring, and grinding to form a modified titanium dioxide deodorizing spray. Alternatively, yttrium oxide is dissolved in ethanol and then added into a colloidal solution together with modified titanium dioxide deodorizing powder or modified titanium dioxide deodorizing paste, and the mixture is stirred and ground.

[0021] The modified titanium dioxide deodorizing powder of the present invention was tested for deodorizing odors in sewage from visceral oil extraction workshops and sewage treatment plants, as well as in septic tanks at chicken farms. The modified titanium dioxide deodorizing paste was diluted with water and then tested for deodorizing odors in workshops, closed rooms, sludge sedimentation tanks and sludge drying areas, slaughterhouses, etc. The modified titanium dioxide deodorizing spray was tested for deodorizing odors in residential areas such as households, nursing homes, student dormitories, and pet feces, all of which achieved excellent deodorizing effects. The present invention transmits ultraviolet light to the backlit surface of the particles through the combined action of a photoinducer and a photoabsorber, greatly improving the photosensitivity and high chemical properties of the titanium dioxide particles, and rapidly enhancing the degradation function of odors or harmful gases. The antibacterial fragrance is applied to residential rooms, and while emitting fragrance, it helps to inhibit and fight bacteria, and works together with yttrium oxide to synergize the modification of the two agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a comparison photo of the sewage decontamination test of the modified titanium dioxide deodorizing powder in Example 3; Figure 2 This is the third-party test data of the modified titanium dioxide deodorizing cream in Example 5 in the deodorizing test in a closed space; Figure 3 Example 8 is the third-party testing data of the modified titanium dioxide deodorizing spray before and after removing formaldehyde in a hotel room. DETAILED DESCRIPTION

[0023] The term "particles" used below refers to micrometer-sized particles with a particle size of 0.1mm to 1mm; the term "microparticles" refers to nanometer-sized particles with a particle size of 1nm to 10nm. The term "powder" used below refers to particles that are bonded together after dipping and drying, and the term "powder" used below refers to particles that are not bonded together. The term "wavelength overlap" used below refers to the presence of ultraviolet light of the same wavelength within the range of two ultraviolet wavelengths. The ultraviolet wavelengths induced or absorbed by the light inducers and light absorbers used in the present invention are shown in the table below:

[0024] The modified titanium dioxide deodorizing product of the present invention is available in three forms: powder, cream, and spray. The product has been developed over three years and has undergone numerous trials. The successful product is described below as an example. For ease of understanding, the main ingredients in the examples are listed in the following table: Example 1: Modified titanium dioxide deodorizing powder

[0025] In this embodiment, the light inducers used are benzoin isopropyl ether and 4-methylbenzophenone, and the light absorber used is methyl o-benzoylbenzoate. Benzoin isopropyl ether can induce ultraviolet light with a wavelength of 200 to 260 nm, and 4-methylbenzophenone can induce ultraviolet light with a wavelength range of 260 to 300 nm. It also self-emits ultraviolet light and can effectively excite TiO2 in a dark light environment. The combination of the two light inducers increases the wavelength of ultraviolet light to 200 to 300 nm, which broadens the wavelength range of ultraviolet light compared to the use of a single light inducer. The methyl o-benzoylbenzoate light absorber has a strong absorption effect on ultraviolet light with a wavelength of 220 to 370 nm, and the wavelength overlap of the two agents is 220 to 300 nm.

[0026] The steps of preparing the modified nano titanium dioxide deodorizing powder in this embodiment include: Step 1: Prepare titanium dioxide particles. This method utilizes a sol-gel process, which is currently available. The most prominent advantage of the sol-gel method for preparing TiO2 photocatalysts is its simplicity and easy control of reaction conditions. The generated titanium dioxide sol is placed in a water bath and evaporated to produce a wet gel. The wet gel is then dried in a drying oven to produce a titanium dioxide xerogel. The xerogel is activated by calcining in a calcining furnace, cooled to room temperature, and then crushed into particles sized between 0.2 mm and 0.8 mm to obtain titanium dioxide particles.

[0027] Step 2: Prepare the modified impregnation solution. Dissolve isopropyl benzoate, 4-methylbenzophenone, and methyl o-benzoylbenzoate in ethanol as the solutes. Stir thoroughly to obtain the modified impregnation solution. The concentration of the modified impregnation solution should be between 25% and 35%.

[0028] The molecular weight of benzoin isopropyl ether is 254, that of 4-methylbenzophenone is 196, and that of methyl o-benzoylbenzoate is 240. When the molar ratio of the photoinducer to the light absorber is 1:1, the combined modification effect is outstanding. The molar ratio of the two is usually controlled to be 1:0.8-1.2. Therefore, when preparing the modified impregnation solution, the molar ratio of benzoin isopropyl ether, 4-methylbenzophenone, and methyl o-benzoylbenzoate should be 1:1:2, and the weight ratio should be 1.2-1.3:1:2.4-2.5.

[0029] Step 3: Prepare modified titanium dioxide powder. The titanium dioxide particles prepared in Step 1 are poured into the modified impregnation solution prepared in Step 2 and stirred for at least 1 hour. The particles are then ground and impregnated in a sand mill or grinder, grinding the titanium dioxide particles into nanoparticles for at least 4 hours. During the grinding and impregnation process, the modified impregnation solution gradually penetrates the surface and cavities of the titanium dioxide particles. After impregnation, the modified impregnation solution is filtered and can be reused. The filtered titanium dioxide particles are dried at 40°C to 80°C. The solutes in the modified impregnation solution (isopropyl benzoin, 4-methylbenzophenone, and methyl o-benzoylbenzoate) adhere to the cavities and surface of the titanium dioxide particles, forming modified titanium dioxide powder.

[0030] To achieve a good modified catalytic effect in the modified titanium dioxide deodorizing powder, the weight ratio of the modified material to the titanium dioxide particles must be controlled. If the titanium dioxide particles are completely impregnated in one step, the weight of 1 kg of titanium dioxide particles after impregnation and drying can increase to over 1.15 kg. This means the weight ratio of the modified material to titanium dioxide particles is 15%, not less than 1:7. If the required weight ratio is not achieved in a single impregnation, re-impregnation or multiple impregnations can be performed.

[0031] Step 4: Grind to obtain modified titanium dioxide deodorizing powder. The modified titanium dioxide powder obtained in step 3 is pulverized to 1-10 nm to produce nano-sized modified titanium dioxide particles, i.e., modified titanium dioxide deodorizing powder. The pulverization method can be ball milling or air jet milling. The purpose of pulverization is to break up the powder and nano-size it. Example 2: Modified titanium dioxide deodorizing cream

[0032] The modified nano titanium dioxide deodorizing powder prepared in Example 1 is poured again into the modified impregnation solution after filtration, stirred evenly, and stirred and impregnated for no less than 2 hours. Then, it is passed through a colloid mill, ground and impregnated for no less than 1 hour, and ground into an impregnation paste. An adhesive and Tween 80 are added to the impregnation paste, stirred evenly, passed through a colloid mill again, ground for no less than 1 hour, and a modified titanium dioxide deodorizing paste is obtained after grinding. Alternatively, an adhesive and Tween 80 can be directly added when the impregnation paste is ground, passed through a colloid mill again, and ground into a modified titanium dioxide deodorizing paste.

[0033] Water-soluble adhesives, such as water glass (sodium silicate) and silica sol, are preferred. Tween 80 is a crosslinking agent and is directly related to dilution with water during subsequent use. If the paste concentration is low, the solvent can be evaporated to form a paste.

[0034] When using the modified titanium dioxide deodorizing paste, it needs to be diluted with water and stirred evenly to dilute the paste into a suspended liquid. Then, use a pressure sprayer to spray the liquid onto indoor walls or roofs. The dilution water acts as a carrier for the particles in the modified titanium dioxide deodorizing paste. After stirring, it imparts good fluidity to the modified titanium dioxide particles, facilitating even spraying. To prevent the precipitation of organic matter such as photoinducers and photoabsorbers during dilution with water, Tween 80 acts as a link between organic and inorganic matter, effectively preventing the precipitation of organic matter. After spraying, the ethanol, Tween 80, and water all evaporate and dry, leaving the adhesive bonding the modified titanium dioxide particles to the wall or roof.

[0035] Examples 1 and 2 were tested simultaneously in a poultry offal oil extraction workshop in Henan Province. After slaughter, the skins and offal of poultry, such as chickens, ducks, and geese, are used to extract oil. The decay of the skins and offal in the workshop's heat exchange pump circulating water caused a severe malodor. The modified titanium dioxide deodorizing powder from Example 1 was added to the workshop's circulating water, evenly spreading it at a rate of 20 kg per ton. After one cycle, the malodor was essentially eliminated. A bowl of circulating water was sniffed through the nose and mouth, revealing no nausea, indicating a significant deodorizing effect. The modified titanium dioxide deodorizing paste from Example 2 was diluted with water in a 1:4 ratio to form a spray. After stirring evenly, a pressure spray pump was used to evenly spray the spray onto the workshop walls, ceiling, and floor, particularly onto the walls and cover plates of the circulating water ditch, at a rate of 300 to 400 g of modified titanium dioxide deodorizing paste per square meter. After spraying for a whole morning, the ceiling was not completely coated, and the workshop was essentially odor-free. Example 3: Modified titanium dioxide deodorizing powder

[0036] The biggest drawback of the above embodiment is the particle size control of the particles, which can only be checked after being pulverized. If the particles do not reach the nanometer level, they need to be re-grinded and reworked, resulting in process waste. This embodiment directly uses nanometer-level particles.

[0037] In this embodiment, the light inducer used is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the light absorber used is 2,4-dihydroxybenzophenone. The wavelength range of ultraviolet light induced by 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is 350-400 nm, while the wavelength range of ultraviolet light absorbed by 2,4-dihydroxybenzophenone is 290-400 nm. The wavelength overlap range of the two agents is 350-400 nm, which is the wavelength of ultraviolet light induced by 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0038] The steps of preparing the modified titanium dioxide deodorizing powder in this embodiment include: Step 1: Preparation of titanium dioxide particles. Same as Example 1, except that the xerogel is pulverized into 1 nm to 10 nm particles after calcination and activation.

[0039] Step 2: Prepare the modified impregnation solution. Mix the solutes, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (2,4,6-trimethylbenzoyl-diphenylphosphine oxide), and the light absorber, 2,4-dihydroxybenzophenone, in acetone. Stir and dissolve until uniform. The resulting solution is the modified impregnation solution. The concentration of the modified impregnation solution is controlled between 18% and 28%.

[0040] The molecular weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is 348, and the molecular weight of 2,4-dihydroxybenzophenone is 214. When the molar ratio of the two agents is 1:1, the combined modification effect is outstanding. The molar ratio of the two agents is usually controlled at 1:0.8-1.2, and when preparing the modified impregnation solution, the weight ratio of the two agents is 1.6-1.7:1.

[0041] Step 3: Prepare modified titanium dioxide powder. Add the titanium dioxide particles prepared in Step 1 to the modified impregnation solution prepared in Step 2 and stir to promote mixing. Stir and impregnate for at least 2 hours. Then, grind and impregnate using a colloid mill or other type of grinder. The nano-sized titanium dioxide particles are chemically dispersed in acetone and mechanically dispersed by stirring. Adding mechanical dispersion during grinding promotes thorough mixing of the particles and the modified impregnation solution, increasing the speed and efficiency of impregnation. The grinding process should last at least 1 hour to ensure complete impregnation. During the stirring and grinding impregnation processes, the modified impregnation solution fully penetrates the pores of the titanium dioxide particles. After impregnation, the modified impregnation solution is filtered and thoroughly dried at 30°C to 60°C. The solute atoms (2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4-dihydroxybenzophenone) in the modified impregnation solution adhere to the surface and pores of the titanium dioxide particles, forming the modified titanium dioxide powder. The filtered modified impregnation solution maintains its concentration and can be reused. The evaporated or volatilized acetone is recovered through the condensation device to avoid waste. If the titanium dioxide particles are completely impregnated, the weight of 1 kg of titanium dioxide particles after impregnation and drying can increase to more than 1.3 kg, that is, the weight ratio of the modified material to the titanium dioxide particles is 30%, not less than 1:4.

[0042] Step 4: Prepare modified titanium dioxide deodorizing powder. The modified titanium dioxide powder prepared in Step 3 is crushed to 1-10 nm to produce modified titanium dioxide microparticles, i.e., modified titanium dioxide deodorizing powder. In this example, nano-sized titanium dioxide microparticles are added directly to the modified impregnation solution. This crushing step only addresses the problem of titanium dioxide microparticle adhesion and does not affect particle size.

[0043] This example was tested on sewage and sludge. Sewage was taken from a sewage treatment plant using a graduated cylinder. Figure 1As shown in the comparison, the left side shows sewage, with floating debris and turbidity. The right side shows the water after adding modified titanium dioxide deodorizing powder. After stirring and stagnating, the water has lost its color, except for sediment at the bottom, and the floating debris is almost gone. Subsequently, the deodorizing agent was sprayed on the raw sludge stored in the organic fertilizer production area, evenly applying approximately 400 grams per square meter of sludge surface area. In less than half an hour, the odor was no longer detectable at a distance of about half a meter from the edge of the sludge storage area, demonstrating a significant deodorizing effect. Example 4: Modified titanium dioxide deodorizing powder

[0044] This example uses purchased titanium dioxide granules or microparticles as the raw material. The photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and the light absorbers are benzophenone and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (UV-320). ethyl 2,4,6-trimethylbenzoylphenylphosphonate induces ultraviolet light with a wavelength of 270-370 nm, benzophenone strongly absorbs ultraviolet light with a wavelength of 260-280 nm, and UV-320 strongly absorbs ultraviolet light with a wavelength of 270-400 nm. The combined use of these two light absorbers broadens the ultraviolet light wavelength range to 260-400 nm. The wavelength overlap between the two agents covers the wavelength range of 270-370 nm for the ultraviolet light induced by the photoinitiator.

[0045] The steps of preparing the modified titanium dioxide deodorizing powder in this embodiment include: Step 1: Prepare titanium dioxide particles. Purchase titanium dioxide particles and crush them into 1nm to 10nm particles, or directly purchase titanium dioxide particles.

[0046] Step 2: Prepare the modified impregnation solution. Combine the solutes, ethyl 2,4,6-trimethylbenzoylphenylphosphonate (TEP), benzophenone, and UV-320 (UV-320) in methanol and stir to dissolve evenly. The resulting solution is the modified impregnation solution, with a concentration of 15% to 25%.

[0047] The molecular weight of ethyl 2,4,6-trimethylbenzoylphenylphosphonate is 316, that of benzoin is 212, and that of UV-320 is 323. When the molar ratio of the two agents is 1:1, the combined modification effect is outstanding. When preparing the modified impregnation solution, the molar ratio of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, benzoin, and UV-320 should be 2:1:1, and the weight ratio should be 3:1:1.5.

[0048] Step 3: Prepare modified titanium dioxide powder. Pour the titanium dioxide particles prepared in Step 1 and the modified impregnation solution prepared in Step 2 into a container and stir to promote mixing. The stirring and impregnation time should be no less than 2 hours. The particles are then ground using a colloid mill or other type of grinder for grinding and impregnation. In this example, the titanium dioxide particles are nanometer-sized. The combined effects of chemical dispersion in methanol, stirring dispersion, and mechanical dispersion through grinding promote thorough mixing of the particles and the modified impregnation solution. Grinding and impregnation help improve impregnation speed and efficiency. The grinding and impregnation time should be no less than 1 hour to ensure complete impregnation. After impregnation, the modified impregnation solution is filtered out and thoroughly dried at 40°C to 70°C. The solute atoms in the modified impregnation solution adhere to the surface and cavities of the titanium dioxide particles, producing modified titanium dioxide powder. If the titanium dioxide particles are completely impregnated in one step, the weight of 1 kg of titanium dioxide particles after impregnation and drying can increase to over 1.2 kg, meaning the weight ratio of modified material to titanium dioxide particles should be no less than 1:5. Similarly, if the required ratio is not achieved in one impregnation, it can be impregnated again, or multiple times, with controlling the weight ratio of the two as the key point of quality control.

[0049] Step 4: Prepare modified titanium dioxide deodorizing powder. Crushing the modified titanium dioxide powder prepared in step 3 into modified titanium dioxide deodorizing powder. Crushing only addresses the problem of titanium dioxide particles clumping together. Example 5: Modified titanium dioxide deodorizing cream

[0050] The light inducer and light absorber used in this embodiment are the same as those in Example 4. The steps of preparing the modified titanium dioxide deodorizing cream in this embodiment include: Step 1: Prepare titanium dioxide particles, as in Example 4.

[0051] Step 2: Prepare the modified impregnation solution. The same as Example 4, except that ethanol is used instead of methanol as the solvent.

[0052] Step 3: Impregnation into an impregnation paste. The stirring, grinding and impregnation are the same as in Example 4, except that the filtering and drying processes are omitted.

[0053] Step 4: Prepare the modified titanium dioxide deodorizing paste. After the impregnation is completed, add the adhesive and silane coupling agent to the impregnated paste, stir evenly, and grind it again in a colloid mill for at least 1 hour to obtain the modified titanium dioxide deodorizing paste.

[0054] In this embodiment, after the modified titanium dioxide deodorizing paste is dried, the weight ratio of the modified material to the titanium dioxide particles is not less than 1:5. The weight ratio of the adhesive to the titanium dioxide particles is not less than 1:20. The amount of silane coupling agent added is 0.1 to 3% of the weight of the adhesive. This example and example 4 were also tested in a chicken farm in Quzhou, Handan (the solvent of the test powder prepared in example 4 was ethanol). In the septic tank of the chicken farm, fermentation produced a foul odor. The modified titanium dioxide deodorizing powder of example 4 was evenly sprayed onto the surface of the septic tank liquid with a jet at a rate of 300 grams per square meter of the surface area of ​​the septic tank liquid. After 10 minutes, no odor could be smelled near the septic tank. In a closed room, the fermented chicken manure was spread on a wooden board. The weight ratio of the paste of this example to the dilution water was 1:6. The paste was sprayed on the floor, walls, roof, and fermented chicken manure in the closed room. There was no odor in the room at that time. Samples were taken and tested by a third party before spraying in the closed room. The deodorizing effect was more than 90% (only for the two gases of ammonia and hydrogen sulfide). The test results are attached. Figure 2 After the test, stir the chicken manure and the odor will be emitted. After 3 minutes, enter the room and no odor can be smelled. Example 6: Modified titanium dioxide deodorizing powder

[0055] This example uses titanium dioxide particles as the raw material, 1-hydroxycyclohexyl phenyl ketone as the light inducer, and benzoyl ketone as the light absorber. The wavelength range of ultraviolet light induced by 1-hydroxycyclohexyl phenyl ketone is 240-280 nm, while the wavelength range of ultraviolet light absorbed by benzoyl ketone is 260-280 nm. The spectral range where the two wavelengths overlap is the wavelength of the light absorber, 260-280 nm.

[0056] The steps of preparing the modified titanium dioxide deodorizing powder in this embodiment include: Step 1: Prepare titanium dioxide particles. Purchase titanium dioxide particles with a size of 1 nm to 10 nm.

[0057] Step 2: Prepare the modified impregnation solution. Mix 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone as solutes in an ethanol solvent, stir and dissolve evenly, and the solution is the modified impregnation solution, with the concentration controlled at 10% to 20%. The molecular weight of 1-hydroxycyclohexyl phenyl ketone is 204, and the molecular weight of diphenyl ketone is 212. When preparing the modified impregnation solution, the molar ratio of the two doses is 1:1, and the weight ratio of the two doses should be selected from 1:1 to 1.1. To reduce the amount of ethanol used and save production costs, deionized water can be used as a diluent. To avoid the precipitation of photoinducers or light absorbers when deionized water is added, a small amount of Tween 80 or silane coupling agent is pre-added to the deionized water.

[0058] Step 3: Prepare modified titanium dioxide powder. Pour the titanium dioxide particles prepared in the first step and the modified impregnation solution prepared in the second step into a container, stir and impregnate for no less than 2 hours. Then grind them with a colloid mill or other type of grinder for grinding and impregnation. The grinding and impregnation time should be no less than 1 hour to ensure complete impregnation. After impregnation, filter out the modified impregnation solution and fully dry it at 40℃~100℃. The solute atoms of the modified impregnation solution will adhere to the surface and cavities of the titanium dioxide particles to obtain modified titanium dioxide powder. If the titanium dioxide particles are completely impregnated in one time, the weight of 1kg of titanium dioxide particles can increase to more than 1.25kg after impregnation and drying, that is, the weight ratio of the modified material to the titanium dioxide particles is no less than 1:4.

[0059] Step 4: Prepare modified titanium dioxide deodorizing powder. The modified titanium dioxide powder prepared in step 3 is crushed into modified titanium dioxide deodorizing powder.

[0060] The modified titanium dioxide deodorizing powder of this embodiment was tested in a 100-square-meter slaughterhouse wastewater pool in a nearby slaughterhouse. The modified titanium dioxide deodorizing powder was evenly sprayed onto the surface of the wastewater in the pool using a jet at a rate of 100 grams per square meter. After 8 minutes, no odor was detected near the pool. Example 7: Modified titanium dioxide deodorizing cream

[0061] In this embodiment, the light inducer used is octyl methoxycinnamate, and the light absorber used is methyl o-benzoylbenzoate. The wavelength range of ultraviolet light induced by octyl methoxycinnamate is 290-330 nm, and the wavelength range of ultraviolet light absorbed by methyl o-benzoylbenzoate is 220-370 nm. The spectral range where the wavelengths of the two agents overlap is the wavelength of the light inducer, 290-330 nm.

[0062] The steps of preparing the modified titanium dioxide deodorizing cream in this embodiment include: Step 1: Prepare titanium dioxide particles. Purchase titanium dioxide particles with a size of 1 nm to 10 nm.

[0063] Step 2: Prepare the modified impregnation solution. Combine octyl methoxycinnamate and methyl o-benzoylbenzoate as solutes in ethanol and stir to dissolve evenly. The resulting solution is the modified impregnation solution. The concentration of the modified impregnation solution is 20% to 25%. To reduce the amount of ethanol used, deionized water can be used as the diluent. A small amount of Tween 80 or a silane coupling agent can be pre-added to the deionized water.

[0064] The molecular weight of octyl methoxycinnamate is 290, and the molecular weight of methyl o-benzoylbenzoate is 240. When the molar ratio of the photoinducer and the light absorber is 1:1, the combined modification effect is outstanding. When preparing the modified impregnation solution, the weight ratio of the two agents should be 1:1.2.

[0065] Step 3: Impregnation: Pour the titanium dioxide particles and modified impregnation solution into a container and stir for at least 2 hours. Then, grind the mixture in a colloid mill for at least 1 hour to ensure complete impregnation.

[0066] Step 4: Prepare the modified titanium dioxide deodorizing paste. Add a binder and a silane coupling agent or Tween 80 to the impregnation paste (this addition can be omitted if a larger amount was added in the modified impregnation solution in step 2). The weight ratio of binder to titanium dioxide particles is preferably 1:12. The crosslinker should be added in an amount of 0.1-3% of the binder weight. After stirring evenly, grind again in a colloid mill for at least 1 hour to obtain the modified titanium dioxide deodorizing paste. The weight ratio of the modified material to titanium dioxide particles should be no less than 1:7.

[0067] This example was tested in a nearby slaughterhouse. The main sources of foul odors were the gutters and fermented grease on the ground. Two days before the inspection by the relevant authorities, during a break in the workshop while cleaning, a spray solution was prepared in a ratio of 1:5 paste to water. The mixture was stirred evenly and applied using a spray pump to the workshop ceiling, walls, floor, and trench walls. Simultaneously, modified titanium dioxide deodorizing powder was sprinkled into the wastewater tank outside the workshop. The workshop was odor-free, earning high praise from the inspectors. Example 8: Modified titanium dioxide deodorizing spray

[0068] In this example, the photoinitiator used octyl methoxycinnamate, and the light absorber used benzophenone. Octyl methoxycinnamate can induce ultraviolet light with a wavelength of 290-330 nm, while benzophenone strongly absorbs ultraviolet light with a wavelength of 260-330 nm, which includes the wavelength of the photoinitiator. The wavelengths of the two agents overlap at 290-330 nm. Borneol was used as the antibacterial fragrance, ethanol was used as the solvent, and diluted with water. A silane coupling agent was used as the crosslinker, and silica sol was used as the adhesive.

[0069] The steps of preparing the modified titanium dioxide deodorizing spray in this embodiment include: Step 1: Prepare titanium dioxide and yttrium oxide particles.

[0070] Step 2: Prepare the modified impregnation solution. Slowly add the methoxycinnamate octyl ester light inducer and benzophenone light absorber to ethanol and stir to dissolve. Then add borneol and continue stirring to dissolve. Ethanol is the solvent, and the light inducer, light absorber, and antibacterial fragrance are the solutes. Once all dissolved, the modified impregnation solution is formed. The concentration of the modified impregnation solution is 15% to 35%.

[0071] The molecular weight of octyl methoxycinnamate is 290, and the molecular weight of benzophenone is 182. When the molar ratio of the two doses is 1:1, the combined modification effect is outstanding. During preparation, the molar ratio of the two doses is usually controlled to be 1:0.8-1.2, and the weight ratio is preferably 1:0.5-0.75. The amount of borneol added is 15%-50% of the weight of the above two doses. The upper limit is taken when a strong aroma is required, and the lower limit is taken when a light aroma is required. In this embodiment, the weights of ethanol, octyl methoxycinnamate, benzophenone, and borneol are 1000g, 120g, 75g, and 40g, respectively.

[0072] Step 3: Prepare the titanium dioxide impregnation solution. Nano-sized titanium dioxide particles and yttrium oxide are gradually added to the modified impregnation solution prepared in Step 2 and stirred. Nano-sized particles tend to agglomerate in liquids, and ethanol helps disperse the particles, resulting in chemical dispersion. However, ethanol dispersion is insufficient for uniform particle distribution, so stirring is required. During the dispersion process, the particles are impregnated and stirred for at least 2 hours. They are then ground in a colloid mill. Grinding and stirring act as a means of further dispersing the particles, resulting in a grinding and impregnation process for at least 1 hour. After stirring and grinding, the ethanol solution containing the dissolved photoinitiator, light absorber, antibacterial fragrance, and yttrium oxide gradually penetrates the surface and cavities of the particles, forming the titanium dioxide impregnation solution. The weight of yttrium oxide in the titanium dioxide particles should not exceed 40%, and the weight ratio of solute (photoinitiator, light absorber, antibacterial fragrance) to particles (titanium dioxide) should be no less than 1:5. In this example, the weights of the nano-sized titanium dioxide particles and yttrium oxide are 800g and 200g, respectively.

[0073] Step 4: Prepare a colloidal solution. Slowly add the silane coupling agent and silica sol to water, stir evenly, and dissolve to form a colloidal solution. The silane coupling agent concentration is 0.2% to 0.8% by weight of the water, with the upper limit being used for higher solution concentrations. The silica sol concentration is 0.2% to 2% by weight of the water, with the upper limit being used when the titanium dioxide particles need to adhere to indoor walls or ceilings for a long time. In this example, the weights of water, silane coupling agent, and silica sol are 80 kg, 200 g, and 600 g, respectively.

[0074] Step 5: Prepare the modified titanium dioxide deodorizing spray. Combine the impregnated titanium dioxide solution prepared in Step 3 with the colloidal solution prepared in Step 4, stir thoroughly, and grind through a colloid mill to produce the modified titanium dioxide deodorizing spray. The modified titanium dioxide deodorizing spray in this example weighed over 82 kg after grinding, with some loss and residue from the colloid mill.

[0075] This embodiment conducts a formaldehyde and ammonia benzene removal test on residents after renovation. The boards used for decoration often emit harmful gases such as formaldehyde and ammonia benzene. The modified titanium dioxide deodorizing spray is placed in a container and sprayed with a spray pump while stirring. Spray at a rate of 0.1 to 0.2 kg of spray per square meter on the wall, ceiling, and home wood surface. There is no odor immediately after spraying. Within one week after spraying, check every day and no odor is detected, only the aroma of borneol. Later, the odor was removed by spraying in a newly renovated hotel. After spraying, the aroma in the room was highly praised by customers, which helped the hotel to open quickly. During the spraying operation, the hotel invited a third party to conduct testing, attached Figure 3 The formaldehyde test results for one room before spraying and another room after spraying. Example 9: Modified titanium dioxide deodorizing spray

[0076] In this embodiment, the light inducers used are phenyl salicylate and 4-methylbenzophenone, and the light absorbers used are benzoyl ketone and methyl o-benzoylbenzoate. Phenyl salicylate can induce ultraviolet light with a wavelength of 290 to 330 nm, while 4-methylbenzophenone induces ultraviolet light with a wavelength range of 260 to 300 nm and self-emitted ultraviolet light, which can effectively excite TiO2 in a dark light environment. The combination of the two light inducers increases the wavelength of the induced ultraviolet light to 260 to 330 nm. Benzoyl ketone has a strong absorption effect on ultraviolet light with a wavelength of 260 to 280 nm, while methyl o-benzoylbenzoate absorbs ultraviolet light with a wavelength of 220 to 370 nm. The combination of the two can strongly absorb ultraviolet light with a wavelength of 220 to 370 nm. The wavelengths of the two agents overlap at 260 to 330 nm, which is the wavelength range of ultraviolet light induced by the combined light inducers. The antibacterial fragrance is storax, the solvent is ethanol, which is diluted with water, the cross-linking agent is silane coupling agent and titanate coupling agent, and the adhesive is 107 glue.

[0077] The steps of preparing the modified titanium dioxide deodorizing spray in this embodiment include: Step 1: Prepare titanium dioxide and yttrium oxide particles. Purchase nano titanium dioxide and yttrium oxide particles from outside.

[0078] Step 2: Prepare the modified impregnation solution. Slowly add the photoinitiator (phenyl salicylate and 4-methylbenzophenone) and the photoabsorber (benzoyl ketone and methyl o-benzoylbenzoate) to ethanol and stir to dissolve. Then, add the antibacterial fragrance (styrax) and continue stirring to dissolve. Ethanol is the solvent, and the photoinitiator, photoabsorber, and antibacterial fragrance are the solutes. Once all dissolved, the modified impregnation solution is formed. The concentration of the modified impregnation solution is 15% to 35%.

[0079] The molecular weights of the light inducers phenyl salicylate and 4-methylbenzophenone are 214 and 196 respectively, and the molecular weights of the light absorbers methyl o-benzoylbenzoate and dibenzoyl ketone are 240 and 212 respectively. When the molar ratio of the two doses is 1:1, that is, the weight ratio of the four is 1.1:1:1.2:1.1, the combined modification effect is outstanding. During preparation, the molar ratio of the two doses is usually controlled to be 1:0.8-1.2, and the amount of storax added is 15%-50% of the weight of the above two doses. In this embodiment, the weights of ethanol, phenyl salicylate, 4-methylbenzophenone, dibenzoyl ketone, methyl o-benzoylbenzoate, and storax are 1kg, 55g, 50g, 60g, 55g, and 80g respectively.

[0080] Step 3: Prepare the impregnation titanium dioxide liquid. Gradually add the nano-titanium dioxide particles and yttrium oxide to the modified impregnation liquid prepared in the second step, and stir and impregnate for not less than 2 hours. The particles are chemically dispersed in ethanol and stirred, and then passed through a colloid mill for grinding, dispersion and impregnation, and the grinding and impregnation is not less than 1 hour. After stirring and impregnation and grinding and impregnation, the solute and yttrium oxide gradually penetrate into the surface and cavities of the particles to form the impregnation titanium dioxide liquid. The weight ratio of yttrium oxide to titanium dioxide particles is not higher than 40%; the weight ratio of solute to titanium dioxide particles is not lower than 1:5. The configuration weights of the nano-titanium dioxide particles and yttrium oxide particles in this embodiment are 700g and 200g, respectively.

[0081] Step 4: Prepare a colloidal solution. Slowly add the silane coupling agent, titanate coupling agent, and 107 glue to water, stir evenly, and dissolve to form a colloidal solution. The silane coupling agent and titanate coupling agent should be present at a concentration of 0.2% to 0.8% by weight of the water, with the lower concentration being used for low solution concentrations. The 107 glue should be present at a concentration of 0.2% to 2% by weight of the water, with the upper concentration being used when long-term titanium dioxide particle adhesion is desired. In this example, the weights of water, silane coupling agent, titanate coupling agent, and 107 glue are 60 kg, 70 g, 70 g, and 1000 g, respectively.

[0082] Step 5: Prepare the modified titanium dioxide deodorizing spray. Combine the impregnated titanium dioxide solution prepared in Step 3 with the colloidal solution prepared in Step 4, stir thoroughly, and grind in a colloid mill to form the modified titanium dioxide deodorizing spray. The modified titanium dioxide deodorizing spray in this example weighs 62.6 kg after grinding.

[0083] The modified titanium dioxide deodorizing spray of this embodiment was tested in a nursing home. A few elderly people had difficulty controlling themselves, causing a serious odor in the room. The modified titanium dioxide deodorizing spray was placed in a container and sprayed with a spray pump while stirring. It was sprayed on the walls and ceilings of the living room. Rooms with severe odor that could not be entered were sprayed twice, and rooms with less severe odor were sprayed once. After spraying, the rooms with less severe odor were free of odor, while the odor in the severe rooms was greatly reduced. However, since the underwear and bedding were not sprayed, there was still a smell. One month later, the fragrance of storax could still be smelled in the room. Example 10: Modified titanium dioxide deodorizing spray

[0084] In this example, the photoinitiators used are octyl methoxycinnamate and 4-methylbenzophenone, and the light absorber is 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (UV-320). Octyl methoxycinnamate induces ultraviolet light with a wavelength of 290 to 330 nm, while 4-methylbenzophenone induces ultraviolet light with a wavelength range of 260 to 300 nm. It also spontaneously emits ultraviolet light, effectively exciting TiO2 in dim light environments. The combination of these two photoinitiators increases the wavelength of the induced ultraviolet light to 260 to 330 nm. 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole (UV-320) strongly absorbs ultraviolet light with a wavelength of 270 to 400 nm. The wavelengths of the two agents overlap, from 270 to 330 nm. The antibacterial flavors are borneol and storax, the solvent is ethanol, which is diluted with water, the cross-linking agent is titanate coupling agent, and the adhesive is water glass.

[0085] Step 1: Prepare titanium dioxide and yttrium oxide particles.

[0086] The steps of preparing the modified titanium dioxide deodorizing spray in this embodiment include: Step 2: Prepare the modified impregnation solution. Slowly add the light inducing agents (octyl methoxycinnamate and 4-methylbenzophenone) and the light absorber (UV-320) to ethanol and stir to dissolve. Then, add the antibacterial flavorings (borneol and styrax) and continue stirring to dissolve. Once dissolved, the modified impregnation solution is obtained. The concentration of the modified impregnation solution is 15% to 35%.

[0087] The molecular weights of the light inducing agents octyl methoxycinnamate and 4-methylbenzophenone are 290 and 196 respectively, and the molecular weight of the light absorber UV-320 is 323. When the molar ratio of the two doses is 1:1, the molar ratio of octyl methoxycinnamate, 4-methylbenzophenone and UV-320 should be 1:1:2, and the weight ratio of the three should be 1.5:1:3.3, and the combined modification effect is outstanding. During preparation, the molar ratio of the two doses is usually controlled to be 1:0.8-1.2. The amount of borneol and storax added is 15%-50% of the weight of the above two doses. In this embodiment, the weights of ethanol, octyl methoxycinnamate, 4-methylbenzophenone, UV-320, borneol and storax are 1kg, 38g, 25g, 83g, 25g and 25g respectively.

[0088] Step 3: Prepare the impregnation titanium dioxide liquid. Gradually add the nano-titanium dioxide particles and yttrium oxide to the modified impregnation liquid prepared in the second step, and stir and disperse them at the same time under the action of ethanol chemical dispersion, and stir and impregnate for no less than 2 hours. Then grind them in a colloid mill, and grind and impregnate for no less than 1 hour. After stirring and impregnation and grinding and impregnation, the photoinitiator, light absorber, antibacterial fragrance and yttrium oxide gradually penetrate into the surface and cavities of the particles to form the impregnation titanium dioxide liquid. The weight ratio of yttrium oxide to the particles (titanium dioxide) is not higher than 40%; the weight ratio of solute (photoinitiator, light absorber, antibacterial fragrance) to particles is not lower than 1:5. The weights of the nano-titanium dioxide particles and yttrium oxide in this embodiment are 600g and 160g, respectively.

[0089] Step 4: Prepare a colloidal solution. Slowly add titanate coupling agent and water glass to water, stir evenly, and dissolve to form a colloidal solution. The titanate coupling agent concentration is 0.2% to 0.8% by weight of water, with the upper limit being used for high solution concentrations. The water glass concentration is 0.2% to 2% by weight of water, with the upper limit being used for long-term titanium dioxide particle adhesion. In this example, the weights of water, titanate coupling agent, and water glass are 60 kg, 350 g, and 1000 g, respectively.

[0090] Step 5: Prepare the modified titanium dioxide deodorizing spray. Combine the impregnated titanium dioxide solution prepared in Step 3 with the colloidal solution prepared in Step 4, stir thoroughly, and grind through a colloid mill to form the modified titanium dioxide deodorizing spray. The modified titanium dioxide deodorizing spray in this example weighs 62.5 kg after grinding.

[0091] At the request of a special education school, this example sprays to remove odors in student dormitories. Some students lack self-care skills, which can lead to unpleasant odors in the dormitories. Use a garden sprayer filled with the spray and apply it to the walls and ceilings of the dormitories, as well as the bathrooms. After spraying, the spray eliminates odors for a long time, retaining the aroma. Example 11: Modified titanium dioxide deodorizing spray

[0092] In this example, the photoinducer is 2-hydroxy-2-methylphenylpropane-1-one, and the light absorbers are benzophenone and methyl o-benzoylbenzoate. 2-hydroxy-2-methylphenylpropane-1-one can induce ultraviolet light with a wavelength of 240-320 nm, while benzophenone and methyl o-benzoylbenzoate absorb ultraviolet light with wavelengths of 260-330 nm and 220-370 nm, respectively. The wavelengths of the two agents overlap at 240-320 nm, which is the wavelength of ultraviolet light induced by the photoinducer. Borneol is used as the antibacterial fragrance, ethanol is used as the solvent, and diluted with water. Tween 80 is used as the crosslinker, and silica sol is used as the adhesive.

[0093] The steps of preparing the modified titanium dioxide deodorizing spray in this embodiment include: Step 1: Prepare titanium dioxide and yttrium oxide particles.

[0094] Step 2: Prepare the modified impregnation solution. Slowly add the photoinitiator (2-hydroxy-2-methylphenylpropane-1-one) and light absorbers (benzophenone and methyl o-benzoylbenzoate) to ethanol and stir to dissolve. Then, add the antibacterial flavoring (borneol) and continue stirring to dissolve. Ethanol is the solvent, and the photoinitiator, light absorber, and antibacterial flavoring are the solutes. Once all dissolved, the modified impregnation solution is formed. The concentration of the modified impregnation solution is 15% to 35%.

[0095] The molecular weight of the photoinducer, 2-hydroxy-2-methylphenylpropane-1-one, is 164, while the molecular weights of the light absorbers, benzophenone and methyl o-benzoylbenzoate, are 182 and 240, respectively. A 1:1 molar ratio of the photoinducer to the light absorber yields a significant combined modification effect. The molar ratio of 2-hydroxy-2-methylphenylpropane-1-one, benzophenone, and methyl o-benzoylbenzoate is preferably 2:1:1, and the weight ratio of the three is preferably 1.8:1:1.3. During preparation, the molar ratio of the two ingredients is typically maintained between 1:0.8 and 1.2. The amount of borneol added should be 15% to 50% of the weight of the two ingredients, with the upper limit being used for stronger aroma and the lower limit for lighter aroma. In this embodiment, the weights of ethanol, 2-hydroxy-2-methylphenylpropane-1-one, benzophenone, methyl o-benzoylbenzoate, and borneol are 2 kg, 140 g, 80 g, 100 g, and 145 g, respectively.

[0096] Step 3: Prepare the impregnation titanium dioxide liquid. Gradually add the nano-titanium dioxide particles and yttrium oxide to the modified impregnation liquid prepared in the second step, and stir and disperse them at the same time under the chemical dispersion effect of ethanol, and stir and impregnate for no less than 2 hours. Then grind them in a colloid mill, and grind and impregnate for no less than 1 hour. After stirring and impregnation and grinding and impregnation, the solute and yttrium oxide gradually penetrate into the surface and cavities of the particles to form the impregnation titanium dioxide liquid. The weight ratio of yttrium oxide to titanium dioxide particles is not higher than 40%; the weight ratio of solute (photoinducer, light absorber, antibacterial fragrance) to particles (titanium dioxide) is not lower than 1:5. The weights of the nano-titanium dioxide particles and yttrium oxide in this embodiment are 1200g and 300g, respectively.

[0097] Step 4: Prepare a colloidal solution. Slowly add Tween 80 and silica sol to water, stir evenly, and dissolve to form a colloidal solution. The Tween 80 concentration is 0.2% to 0.8% by weight of the water, with the lower limit being used for low solution concentrations. The silica sol concentration is 0.2% to 2% by weight of the water, with the lower limit being used when long-term adhesion of titanium dioxide particles is not desired. In this example, the weights of water, Tween 80, and silica sol are 120 kg, 280 g, and 250 g, respectively.

[0098] Step 5: Prepare the modified titanium dioxide deodorizing spray. Mix the impregnated titanium dioxide solution prepared in Step 3 with the colloidal solution prepared in Step 4, stir thoroughly, and grind in a colloid mill to form the modified titanium dioxide deodorizing spray. The modified titanium dioxide deodorizing spray in this example weighs approximately 123 kg after grinding.

[0099] This example uses a large amount of antibacterial fragrance, which is on the upper limit, while the amount of silica sol is low, which is on the lower limit. This makes it suitable for deodorizing pet feces odors in rooms. After a pet defecates on cat litter, spraying the product on the litter is sufficient. Cat litter typically requires cleaning, so the adhesion requirements for the modified titanium dioxide powder are not high. Within a week after the test spraying, the room was free of pet feces odor and the fragrance remained.

[0100] For the convenience of comparison and understanding, the material ratios in the above-mentioned modified titanium dioxide deodorizing spray embodiment are summarized in the following table:

[0101] It should be noted that: 1) The modified titanium dioxide deodorizing paste can be prepared using modified titanium dioxide deodorizing powder as the raw material. The adhesive and cross-linking agent are added to water, stirred evenly, and an adhesive solution is prepared. The modified titanium dioxide deodorizing powder is added to the adhesive solution, stirred and ground. 2) The modified titanium dioxide deodorizing spray can be prepared using modified titanium dioxide deodorizing powder or paste as the raw material. After yttrium oxide is dissolved in ethanol, it is added to the colloidal solution together with the modified titanium dioxide deodorizing powder or paste, stirred and ground. 3) The concentration of the modified impregnation liquid is the empirical data that can meet the weight ratio of titanium dioxide and modified materials in the modified titanium dioxide deodorizing product after one complete impregnation, or meet the fluidity conditions of grinding. The weight ratio after impregnation and drying is the key point of quality control and directly affects the deodorizing effect. High or low concentrations of the modified impregnation liquid affect the impregnation efficiency. 4) The present invention does not involve the concentration of the impregnation paste and the modified titanium dioxide deodorizing paste, but uses the weight ratio of titanium dioxide particles, modified materials and inorganic adhesives as the quality control point. The evaporation of the solvent in the impregnation paste changes the concentration, and the modified titanium dioxide deodorizing paste is diluted with water to facilitate spraying, so the concentration is not a key point. The amount of titanium dioxide particles added is determined based on the weight of the modified material in the modified impregnation liquid, and the amount of adhesive added is determined based on the amount of titanium dioxide particles added, thereby indirectly requiring the concentration of the impregnation paste and the modified titanium dioxide deodorizing paste. 5) When preparing the spray, the antibacterial fragrance is dissolved in the modified impregnation liquid, and can also be dissolved in the impregnating titanium dioxide liquid. No matter how it is dissolved, it is dissolved in the solvent and impregnated on the surface and in the cavities of the titanium dioxide.

Claims

1. A modified titanium dioxide deodorizing product, available in three forms: powder, paste and spray, characterized by: It is formed by impregnating titanium dioxide particles with a modified impregnation liquid; the modified impregnation liquid is a solution of a modified material dissolved in a water-soluble organic solvent; the modified material includes a light inducer and a light absorber, the molar ratio of the light inducer to the light absorber is 1:0.8-1.2, and the wavelengths of the induced ultraviolet rays of the light inducer and the absorbed ultraviolet rays of the light absorber overlap; after the titanium dioxide particles are impregnated and dried, the modified material adheres to the surface and cavities of the titanium dioxide particles, and the weight ratio of the modified material to the titanium dioxide particles is not less than 1:

7.

2. A modified titanium dioxide deodorizing product according to claim 1, characterized in that: The photoinducer is one or more of benzoin isopropyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 4-methylbenzophenone, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, phenyl salicylate, methoxycinnamic acid octyl ester, and 2-hydroxy-2-methylphenylpropane-1-one.

3. A modified titanium dioxide deodorizing product according to claim 1, characterized in that: The light absorber is one or more of benzophenone, methyl o-benzoylbenzoate, 2,4-dihydroxybenzophenone, UV-320, and benzophenone.

4. A modified titanium dioxide deodorizing product according to claim 1, characterized in that: The concentration of the modified impregnation liquid is 10% to 35%; the water-soluble organic solvent is one or more of methanol, ethanol, acetone and glycerol; when the water-soluble organic solvent is replaced by water, a cross-linking agent is added.

5. A modified titanium dioxide deodorizing product according to claim 4, characterized in that: The paste also contains a water-soluble adhesive and a cross-linking agent; the weight ratio of the water-soluble adhesive to the titanium dioxide particles is not less than 1:20, and the amount of the cross-linking agent added is 0.1% to 3% of the weight of the adhesive.

6. A modified titanium dioxide deodorizing product according to claim 4, characterized in that: The spray also contains antibacterial fragrance, yttrium oxide, water-soluble adhesive, cross-linking agent and water; the amount of the antibacterial fragrance added is 15% to 50% of the weight of the photoinducer and the light absorber; the weight ratio of the total weight of the photoinducer, the light absorber and the antibacterial fragrance in the modified impregnation solution to the titanium dioxide particles is not less than 1:5; the weight ratio of yttrium oxide to titanium dioxide particles is not higher than 40%; the cross-linking agent and adhesive are 0.2% to 0.8% and 0.2% to 2% of the weight of water respectively.

7. A modified titanium dioxide deodorizing product according to claim 6, characterized in that: The antibacterial fragrance is styrax, borneol or a combination of the two.

8. The method for preparing the modified titanium dioxide deodorizing powder of claim 4, comprising the following steps: 1) Prepare titanium dioxide particles: prepare titanium dioxide particles by sol-gel method or purchase titanium dioxide particles from outside, and crush them into particles; or purchase titanium dioxide particles from outside; 2) Preparation of modified impregnation liquid: stirring and dissolving the modified material in a water-soluble organic solvent or a mixture of a water-soluble organic solvent and water, stirring evenly to prepare a modified impregnation liquid; 3) Preparation of modified titanium dioxide powder: mixing titanium dioxide particles with the modified impregnation liquid, stirring and impregnating, grinding and impregnating, filtering and drying to obtain modified titanium dioxide powder; 4) Preparation of modified titanium dioxide deodorizing powder: the modified titanium dioxide powder is crushed to obtain modified titanium dioxide deodorizing powder.

9. The method for preparing the modified titanium dioxide deodorizing cream of claim 5, comprising the following steps: 1) Prepare titanium dioxide particles: prepare titanium dioxide particles by sol-gel method or purchase titanium dioxide particles from outside, and crush them into particles; or purchase titanium dioxide particles from outside; 2) preparing a modified impregnation liquid: stirring and dissolving the modified material in a water-soluble organic solvent or a mixture of a water-soluble organic solvent and water, stirring evenly, and preparing a modified impregnation liquid; 3) impregnating into an impregnation paste: mixing titanium dioxide particles with the modified impregnation liquid, and impregnating into an impregnation paste through stirring, impregnation and grinding; 4) preparing a modified titanium dioxide deodorizing paste: adding an adhesive and a cross-linking agent to the impregnation paste, stirring and grinding, and obtaining a modified titanium dioxide deodorizing paste; Alternatively, the adhesive and the cross-linking agent are added to water, stirred evenly, to prepare an adhesive solution, and the powder in claim 4 is added to the adhesive solution, stirred and ground to obtain the modified titanium dioxide deodorizing paste.

10. The method for preparing the modified titanium dioxide deodorizing spray according to claim 6, comprising the following steps: 1) preparing titanium dioxide particles and yttrium oxide particles; 2) preparing a modified impregnation solution: dissolving a light inducer, a light absorber and an antibacterial fragrance in a water-soluble organic solvent or a mixture of a water-soluble organic solvent and water by stirring, and uniformly stirring to prepare a modified impregnation solution; 3) Preparation of titanium dioxide impregnation liquid: adding titanium dioxide particles and yttrium oxide particles into the modified impregnation liquid and stirring, after stirring impregnation and grinding impregnation, the light inducer, light absorber, antibacterial fragrance and ethanol solution of yttrium oxide dissolved gradually penetrate into the surface and cavities of the particles to form the titanium dioxide impregnation liquid; 4) Preparation of colloidal solution: adding water-soluble adhesive and cross-linking agent into water, stirring evenly, and dissolving to form a colloidal solution; 5) Making modified titanium dioxide deodorizing spray: mixing the impregnated titanium dioxide liquid with the colloidal solution, stirring, and grinding into modified titanium dioxide deodorizing spray; Alternatively, yttrium oxide is dissolved in ethanol and then added into a colloidal solution together with the powder of claim 4 or the paste of claim 5, and the mixture is stirred and ground.

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