CN114931982A - Composite titanium dioxide photocatalytic concentrated solution, photocatalytic digestion membrane and preparation method thereof - Google Patents
Composite titanium dioxide photocatalytic concentrated solution, photocatalytic digestion membrane and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
The invention provides a composite titanium dioxide photocatalytic concentrated solution, a photocatalytic digestion membrane and a preparation method thereof. The composite titanium dioxide photocatalytic concentrated solution is prepared from the following raw materials in percentage by mass: 5.0-50.0 percent of titanium dioxide nano particles, 5.0-30.0 percent of porous adsorbing material, 1.0-5.0 percent of sodium alginate, 10.0-50.0 percent of inorganic adhesive and the balance of water. According to the composite titanium dioxide photocatalytic concentrated solution, the sodium alginate water-soluble polymer is added to wrap and protect titanium dioxide nano particles, so that the titanium dioxide nano particles in the system are prevented from being contacted with each other, the stability of the system is improved, and the sedimentation of the titanium dioxide nano particles is prevented; and through the selection of the types of the inorganic adhesive in the concentrated solution and the control of the percentage content of each component in the concentrated solution, the concentrated solution has proper viscosity, the occurrence of sedimentation is avoided, and the processing is facilitated, so that the content of titanium dioxide nanoparticles in the product is greatly increased on the premise of ensuring the stability of a system, and the catalytic performance of the photocatalytic digestion membrane is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite titanium dioxide photocatalytic concentrated solution, a photocatalytic digestion membrane and a preparation method thereof.
Background
Anatase titanium dioxide nanoparticles are widely used as common photoresponse components in a variety of photocatalytic products. Compared with common rutile titanium dioxide nanoparticles, the anatase titanium dioxide nanoparticles have a narrower band gap structure, and valence band electrons of the anatase titanium dioxide nanoparticles can be excited by ultraviolet light with the wavelength of less than 385.5nm to generate photogenerated electron-hole pairs. The photo-generated electrons and the holes react with oxygen molecules and water molecules which are abundant in the environment to further generate O with strong oxidizing property 2 · - And OH - Free radicals capable of oxidative decomposition of various atmospheric pollutants to H 2 O、CO 2 Or substances harmless to the environment such as inorganic salts.
The ultraviolet band energy in sunlight is only about 4% of the full-band energy, so in order to achieve the best purification effect on the atmospheric pollutants, a large-scale three-dimensional photocatalytic system needs to be constructed in an urban air duct through which the atmospheric pollutants pass. Among them, it has been proved to be an effective method to form a photocatalytic digestion film containing anatase-type titanium dioxide nanoparticles on the surface of an air duct by performing a coating operation on the bottom surface (e.g., road, etc.) and the side surface (e.g., facade, ceiling, etc.) of an urban air duct using a photocatalytic nano digestion solution.
The photocatalytic stock solution containing anatase titanium dioxide nanoparticles is generally coated on the surface of a building to form a titanium dioxide nano photocatalytic digestion film. At present, the titanium dioxide nano photocatalytic stock solution still has the following problems: the titanium dioxide photocatalysis stock solution can generate the phenomenon of sedimentation and hardening in the long-term storage process, and the normal use of the product is seriously influenced. The titanium dioxide nanoparticles have higher specific surface energy, the surface energy is easily reduced through agglomeration to reach a stable state, the particle size and the mass of particles in a system are gradually increased and finally settled to the bottom of the system, and the settled titanium dioxide nanoparticles are coagulated and hardened with other components in the solution, such as an adhesive, a dispersing agent and the like, under the interaction. Even if the hardened products are dispersed again, the products cannot be restored to the state before hardening, and a series of serious negative results such as equipment failure in the construction process, low catalytic performance of the formed digestion membrane and the like can be caused. On the other hand, in order to improve the catalytic performance of the photocatalytic digestion membrane, it is necessary to increase the concentration of titanium dioxide in the photocatalytic stock solution. The photocatalysis stock solution is concentrated and diluted when in use, and the control of the content of the titanium dioxide in the digestion membrane can be more conveniently realized by adjusting the dilution rate. However, the concentrated photocatalytic stock solution can generate more serious sedimentation-hardening phenomenon due to overhigh concentration of particles in the storage process, and cannot be smoothly applied to the normal construction process of the digestion membrane.
In order to further improve the stability of the photocatalytic system and to prolong its storage time, the following two methods are mainly used: the first is to make a precise adjustment of the pH of its aqueous solution. This is because a large number of-OH residues exist on the surface of the titanium dioxide nanoparticles, and in an aqueous solution, these-OH residues ionize a small amount of hydrogen ions (H) + ) The solution is rendered weakly acidic. The control of the surface charge state of the titanium dioxide nanoparticles can be realized by accurately adjusting the pH value of the solution. It was found that-OH residue on the surface of anatase type titanium dioxide nanoparticles can be largely ionized to-O at pH 6.8 - The particle surface is negatively charged. The negatively charged surface can largely adsorb cations in the solution, and an electric double layer structure is formed around the nano-particles. The electrostatic repulsion of the double electric layers reduces the collision among particles, and the effect of suspending the titanium dioxide nano particles in the solution for a long time can be achieved. However, the method has high requirement on the pH value of the solution, and when the system components are complex, the pH value of the system is difficult to accurately adjust, so that the production difficulty of the product is greatly increased. The second method is to modify the surface of the nano-particles by using a dispersing agent, wherein-OH residues on the surface of the titanium dioxide nano-particles adsorb polar molecules (dispersing agent) in the solution, a charged layer is formed on the surface layer of the nano-particles, and the particles are prevented from agglomerating by electrostatic repulsion, so that the stability of the titanium dioxide nano-particles in the aqueous solution is improved. But instead of the other end of the tubeWhen the system components are complex, other ions existing in the solution in large quantity can generate competitive adsorption effect with the dispersant, the surface modification effect is influenced, and the agglomeration-sedimentation phenomenon still occurs.
Therefore, for the photocatalytic liquid containing titanium dioxide nanoparticles, the bottleneck problem of improving the catalytic performance of the photocatalytic digestion solution at present is how to increase the effective content of the titanium dioxide nanoparticles and the stability of the product, and prolong the service life of the product.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a composite titanium dioxide photocatalytic concentrated solution, a photocatalytic digestion membrane and a preparation method thereof, wherein a water-soluble high molecular compound sodium alginate is added into a system to wrap and protect titanium dioxide nano particles, so that the direct collision of the titanium dioxide nano particles in the system is effectively prevented, the stability of the system is increased, the suspension state of the titanium dioxide nano particles can be kept for a long time, and the particle aggregation-sedimentation-hardening process in the system is effectively prevented; and through the selection of the types of the inorganic adhesive in the concentrated solution and the control of the percentage content of each component in the concentrated solution, the concentrated solution has proper viscosity, is more convenient to process, successfully realizes the large increase of the titanium dioxide content in the product on the premise of ensuring the stability of the system, and improves the catalytic performance of the photocatalytic digestion membrane.
In order to solve the above problems, one aspect of the present invention provides a composite titanium dioxide photocatalytic concentrated solution, which comprises the following raw materials, by mass:
5.0-50.0 percent of titanium dioxide nano particles, 5.0-30.0 percent of porous adsorbing material, 1.0-5.0 percent of sodium alginate, 10.0-50.0 percent of inorganic adhesive and the balance of water.
Compared with the existing commonly used photocatalytic stock solution, the composite titanium dioxide photocatalytic concentrated solution has the advantages that the content of titanium dioxide nanoparticles in the concentrated solution is greatly increased, the photocatalytic performance of the concentrated solution can be improved by increasing the content of the titanium dioxide nanoparticles, and in addition, because the dilution process is controllable, the titanium dioxide content of the prepared digestion membrane can be accurately controlled by adjusting the dilution rate according to the catalytic performance requirement during use. Furthermore, because titanium dioxide nanoparticles are easy to agglomerate to cause sedimentation, sodium alginate is added into the concentrated solution. Sodium alginate is an industrial product extracted from seaweed, is widely applied to the fields of food and medicine, and is a natural polysaccharide compound with good water solubility. After the sodium alginate is dissolved in water, the molecular skeleton wraps the titanium dioxide nano particles, the stability of the system is improved by preventing the particles from mutually contacting and colliding, the suspension state of the titanium dioxide nano particles is kept for a long time, and the storage time of the product is greatly prolonged.
Wherein, the selection of the mass percent of each component has obvious influence on the catalytic performance of the product, the viscosity, the stability and the processability of the system. As described above, the lower the content of titanium dioxide nanoparticles, the poorer the catalytic performance of the photocatalytic digestion membrane prepared, and the higher the content, the easier the agglomeration to cause the sedimentation. To porous adsorption material, its content is too much, can cause to clear up the membrane thickly, influences the absorption efficiency of titanium dioxide to ultraviolet band light in the sunshine, and gaseous pollutant is adsorbed the back and can't in time obtain purifying simultaneously, when environmental factor such as humiture changes, the adsorbed pollutant is released in the pore, easily causes secondary pollution, and the content is low then can reduce to clear up the degradation rate of membrane to gaseous pollutant. For sodium alginate, a small amount of sodium alginate can not completely wrap titanium dioxide nanoparticles, so that the system can be only transiently stabilized, the solution after standing still can be precipitated and hardened, and the increase of the sodium alginate content can adsorb a large amount of water molecules around a molecular skeleton, so that the viscosity of the system is too high, the flowability of the product is influenced, and subsequent processing cannot be performed. The viscosity of the concentrated solution is also significantly affected by the inorganic binder and water, and the content of the inorganic binder is too high, so that the concentrated solution is too thick to be processed, and too low, so that the residual content of the concentrated solution after dilution during use is very small, and the concentrated solution cannot perform expected functions in the process of forming a digestion membrane. Repeated experiments show that the obtained composite titanium dioxide photocatalytic concentrated solution has good catalytic performance, viscosity, stability, processability and the like when the mass fractions of the components are adopted.
Preferably, the preparation raw materials comprise the following components in percentage by mass:
10.0-30.0 percent of titanium dioxide nano particles, 10.0-20.0 percent of porous adsorbing material, 1.0-3.0 percent of sodium alginate, 10.0-30.0 percent of inorganic adhesive and the balance of water.
A large number of experimental researches show that when the components are adopted in percentage by mass, the obtained titanium dioxide photocatalytic concentrated solution has better catalytic performance, more appropriate viscosity, easy processing and better stability, and can be stored for a long time.
Preferably, the titanium dioxide nanoparticles are a mixture of rutile titanium dioxide and anatase titanium dioxide, and the mass percentage of the anatase titanium dioxide is 70% -90%. Through a large number of experiments of the inventor, the anatase titanium dioxide can be enabled to have the best photocatalytic performance when the mass percent of the anatase titanium dioxide is 70-90%.
Preferably, the titanium dioxide nanoparticles have a particle size of 20-50 nm.
Preferably, the porous adsorption material is a material with micropores or mesopores, and the material is one or a mixture of more of silicate materials, aluminosilicate materials, porous carbon materials and metal-organic framework materials. Silicate-based materials such as diatomaceous earth, zeolites, molecular sieves, and the like, aluminosilicate-based materials such as kaolin, bentonite, montmorillonite, and the like, metal-organic framework (MOF) or Covalent Organic Framework (COF) materials such as MOF-5, HKUST-1, MIL-100, and the like.
Preferably, the particle fineness of the porous adsorption material is more than 300 meshes.
Preferably, the inorganic binder is one or a mixture of sodium silicate, solid sodium silicate and liquid sodium silicate.
Wherein, preferably, the inorganic binder is one or the mixture of two of solid sodium silicate and liquid sodium silicate.
After the solution obtained by diluting the photocatalytic concentrated solution is used for surface construction, sodium silicate contained in the solution can absorb CO widely existing in the air 2 、SO 2 When acid gas or Ca existing in large amount in natural environment 2+ 、Mg 2+ The plasma is combined and solidified, and finally the porous silicate structure with the bonding effect is formed through dehydration, so that the titanium dioxide nano particles are firmly attached to the construction surface, and the purpose of enhancing the adhesive force of the titanium dioxide nano particles on the surface is achieved. The sodium silicate is a solid or liquid industrial product prepared from silicon dioxide and soda ash through a series of processes such as high-temperature firing and the like, and is widely applied to multiple industrial fields such as papermaking, building, textile and the like. The chemical composition of natron can be expressed as Na 2 O·mSiO 2 ·nH 2 O, where m (modulus) is the difference between natron and the strict chemical sodium silicate (i.e. sodium metasilicate nonahydrate, Na) 2 SiO 3 ·9H 2 O, CAS number 13517-24-3). The national standard of the people's republic of China (GB/T4209-. The sodium silicate has faster curing speed and stronger adhesive force compared with the strict chemical sodium silicate. On the other hand, the sodium silicate has good affinity and faster curing speed for most construction surface materials, such as cement roads, walls and the like, compared with other types of inorganic binders, such as calcium hydroxide, and the sodium silicate can be used for quickly and firmly bonding each solid component in the titanium dioxide photocatalysis stock solution to the construction surface by using a smaller amount of sodium silicate. The sodium silicate is used as the adhesive, so that the wear resistance of the digestion film is improved, the service life is prolonged, and the functional influence on the construction surface can be minimized.
In another aspect of the present invention, a method for preparing the above-mentioned composite titanium dioxide photocatalytic concentrated solution is provided, which is characterized by comprising the following steps:
and mixing the preparation raw materials of the composite titanium dioxide photocatalytic concentrated solution to obtain the composite titanium dioxide photocatalytic concentrated solution.
The invention further provides a titanium dioxide photocatalytic digestion membrane prepared from the composite titanium dioxide photocatalytic concentrated solution.
In another aspect, the invention provides a method for preparing the titanium dioxide photocatalytic digestion membrane, which comprises the following steps:
and (3) diluting the compound titanium dioxide photocatalytic concentrated solution, then coating the diluted compound titanium dioxide photocatalytic concentrated solution on the surface and drying to obtain the titanium dioxide photocatalytic digestion membrane.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the existing commonly used photocatalytic stock solution, the composite titanium dioxide photocatalytic concentrated solution has the advantages that the content of titanium dioxide nanoparticles in the concentrated solution is greatly improved, the photocatalytic performance of the composite titanium dioxide photocatalytic concentrated solution can be improved by increasing the content of the titanium dioxide nanoparticles, and the content of titanium dioxide in the prepared digestion membrane can be controlled by adjusting the dilution rate according to the catalytic performance requirement during use because the dilution process is controllable.
2. Because titanium dioxide nano particles are easy to agglomerate to cause sedimentation, the composite titanium dioxide photocatalytic concentrated solution disclosed by the invention is prepared by adding sodium alginate into the concentrated solution, wherein the sodium alginate is a natural polysaccharide water-soluble high-molecular compound, and after the sodium alginate is dissolved in water, a molecular skeleton extends in the solution to wrap the titanium dioxide nano particles, so that the stability of the system can be increased by preventing the titanium dioxide nano particles in the system from mutually contacting and colliding, and the suspension state of the titanium dioxide nano particles is kept for a long time, thereby improving the stability of the concentrated solution and prolonging the storage time of the concentrated solution.
3. The selection of the mass percentages of the components has a significant influence on the catalytic performance of the product, the viscosity, the stability and the processability of the system. As described above, the lower the content of the titanium dioxide nanoparticles, the poorer the catalytic performance of the photocatalytic digestion membrane prepared, and the more the content, the more easily the titanium dioxide nanoparticles are agglomerated to cause sedimentation. To porous adsorption material, its content is too much, can cause to clear up the membrane thickly, influences the absorption efficiency of titanium dioxide to ultraviolet band light in the sunshine, and gaseous pollutant is adsorbed the back and can't in time obtain purifying simultaneously, when environmental factor such as humiture changes, the adsorbed pollutant is released in the pore, easily causes secondary pollution, and the content is low then can reduce to clear up the degradation rate of membrane to gaseous pollutant. For sodium alginate, a small amount of sodium alginate can only enable a solution system to be temporarily stable, the solution after standing still can be precipitated and hardened, and the increase of the content of sodium alginate can adsorb a large amount of water molecules around a molecular skeleton, so that the viscosity of the system is too high, the flowability of a product is influenced, and subsequent processing cannot be performed. The viscosity of the concentrated solution can be obviously influenced by the inorganic binder and water, the content of the inorganic binder is too high, so that the concentrated solution is too viscous to process, and the residual content of the inorganic binder is too low after dilution in use, so that the inorganic binder cannot play a role in forming a digestion membrane. Through repeated experiments, the invention discovers that the obtained composite titanium dioxide photocatalytic concentrated solution has good catalytic performance, viscosity, stability, processability and the like when the components are adopted in parts by weight.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the sources of the raw materials are:
p25 titanium dioxide powder was purchased from the German industry group (Evonik Industries AG); rutile titanium dioxide powder was purchased from Longbai group GmbH; anatase titanium dioxide powder was purchased from Yumengyi Silene titanium dioxide manufacturing Co., Ltd;
the sodium silicate is purchased from Tianjin Zhongshengtai chemical company, and the modulus is 2.85;
the activated carbon powder is purchased from Zhejiang Wanglin Biotech Co., Ltd; sodium hydroxyethyl cellulose and molecular sieve 13X were purchased from Kyong chemical Co., Ltd of Shanghai; polyvinyl alcohol (1750. + -. 50) was purchased from the national pharmaceutical group, Inc.
Example 1
The composite titanium dioxide photocatalytic concentrated solution described in this embodiment is prepared from the following raw materials by mass:
10% of titanium dioxide nano particles, 13X 20% of porous adsorption material molecular sieve, 1% of sodium alginate, 20% of inorganic adhesive sodium silicate and the balance of water.
Wherein the titanium dioxide nano-particles are a mixture of rutile type titanium dioxide and anatase type titanium dioxide, and the mass percent of the anatase type titanium dioxide is 80%; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide of the embodiment comprises the following steps:
dissolving sodium alginate solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected molecular sieve powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to obtain a suspension 1;
step three, adding inorganic adhesive solid into the suspension 1 in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the turbid liquid 3 obtained in the step four by using a homogenizer to finally obtain white thick slurry which is a finished product of the composite titanium dioxide photocatalytic concentrated liquid.
Example 2
The composite titanium dioxide photocatalytic concentrated solution described in this embodiment is prepared from the following raw materials by mass:
20% of titanium dioxide nano particles, 20% of porous adsorption material diatomite powder, 2% of sodium alginate, 10% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide nano-particles are a mixture of rutile type titanium dioxide and anatase type titanium dioxide, and the mass percent of the anatase type titanium dioxide is 80%; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the diatomite powder is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide of the embodiment comprises the following steps:
dissolving sodium alginate solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected diatomite powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to finally obtain a suspension 1;
step three, adding inorganic adhesive solid into the suspension 1 in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four by using a homogenizer to finally obtain offwhite slurry which is a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Example 3
The composite titanium dioxide photocatalytic concentrated solution described in this embodiment is prepared from the following raw materials by mass:
30% of titanium dioxide nano particles, 20% of porous adsorption material activated carbon powder, 2% of sodium alginate, 30% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein, the titanium dioxide nano particles are commercial P25 titanium dioxide powder, wherein, the content of anatase titanium dioxide is 79 percent, and the content of rutile titanium dioxide is 21 percent; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the activated carbon powder is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide comprises the following steps:
dissolving sodium alginate solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected activated carbon powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to obtain a suspension 1;
step three, adding the inorganic adhesive solid into the suspension 1 obtained in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four for 2 hours by using a homogenizer to finally obtain a uniform-texture black-gray product which is a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Example 4 the composite titanium dioxide photocatalytic concentrated solution according to the embodiment is prepared from the following raw materials in percentage by mass:
5% of titanium dioxide nano particles, 13X 5% of porous adsorption material molecular sieve, 3% of sodium alginate, 30% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein, the titanium dioxide nano particles are commercially available P25 titanium dioxide powder, wherein the content of anatase titanium dioxide is 79 percent, and the content of rutile titanium dioxide is 21 percent; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide of the embodiment comprises the following steps:
dissolving sodium alginate solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected molecular sieve 13X powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to obtain a suspension 1;
step three, adding the inorganic adhesive solid into the suspension 1 obtained in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four for 2 hours by using a homogenizer to finally obtain white slurry with uniform texture, namely a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Example 5
The composite titanium dioxide photocatalytic concentrated solution described in this embodiment is prepared from the following raw materials by mass:
40% of titanium dioxide nano particles, 30% of porous adsorption material activated carbon powder, 5% of sodium alginate, 20% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein, the titanium dioxide nano particles are commercially available P25 titanium dioxide powder, wherein the content of anatase titanium dioxide is 79 percent, and the content of rutile titanium dioxide is 21 percent; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the activated carbon powder is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide of the embodiment comprises the following steps:
dissolving sodium alginate solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected activated carbon powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to obtain a suspension 1;
step three, adding the inorganic adhesive solid into the suspension 1 obtained in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four for 2 hours by using a homogenizer to finally obtain viscous black gray slurry with uniform texture, namely a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Comparative example 1
The composite titanium dioxide photocatalytic concentrated solution of the comparative example is prepared from the following raw materials in percentage by mass:
10% of titanium dioxide nano particles, 13X 20% of porous adsorption material molecular sieve, 1% of sodium hydroxyethyl cellulose, 40% of inorganic adhesive sodium silicate and the balance of water.
Wherein the titanium dioxide nano particles are a mixture of rutile type titanium dioxide and anatase type titanium dioxide, and the mass percent of the anatase type titanium dioxide is 80%; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the molecular sieve 13X is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide of the embodiment comprises the following steps:
dissolving sodium hydroxyethyl cellulose solid in a small amount of water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected molecular sieve powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to obtain a suspension 1;
step three, adding inorganic adhesive solid into the suspension 1 obtained in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four by using a homogenizer to finally obtain white thick slurry which is a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Comparative example 2
The composite titanium dioxide photocatalytic concentrated solution of the comparative example is prepared from the following raw materials in percentage by mass:
20% of titanium dioxide nano particles, 20% of porous adsorption material diatomite powder, 2% of polyvinyl alcohol, 25% of inorganic adhesive solid sodium silicate and the balance of water.
Wherein the titanium dioxide nano-particles are a mixture of rutile type titanium dioxide and anatase type titanium dioxide, and the mass percent of the anatase type titanium dioxide is 80%; the particle size of the titanium dioxide nano particles is 20-50 nm; the fineness of the diatomite powder is more than 300 meshes.
The preparation method of the photocatalytic concentration of the composite titanium dioxide comprises the following steps:
dissolving polyvinyl alcohol solid in a small amount of hot water, and stirring by using a mechanical stirrer to obtain a uniform solution;
step two, slowly adding the selected titanium dioxide nanoparticles and the selected diatomite powder into the uniform solution obtained in the step one for multiple times, and continuously stirring to finally obtain a suspension 1;
step three, adding inorganic adhesive solid into the suspension 1 obtained in the step two, and continuously stirring to obtain a suspension 2;
step four, adding water into the suspension 2 obtained in the step three until the components reach the corresponding proportion, and continuously stirring to obtain a suspension 3;
and step five, homogenizing the suspension 3 obtained in the step four by using a homogenizer to finally obtain offwhite slurry which is a finished product of the composite titanium dioxide photocatalytic concentrated solution.
Titanium dioxide photocatalytic digestion membrane performance test
The composite titanium dioxide photocatalytic concentrated solutions obtained in the above examples and comparative examples were diluted with pure water at a ratio of 1: 4. Then 5X 10cm perpendicular to the surface area with a spray gun 2 And repeatedly spraying the diluent on the cement sample piece for 3 times, and drying for 48 hours to obtain the titanium dioxide photocatalytic digestion membrane test sample piece.
The photocatalytic performance test is carried out on the test samples obtained in the examples and the comparative examples, and specifically comprises the following steps: the photocatalytic performance of the test sample piece was tested using acetaldehyde standard gas as the test gas. The test conditions were: acetaldehyde concentration of 1.67ppm, gas humidity of 50%, gas flow rate of 300mL/min, and ultraviolet light intensity of 1mW/cm 2 。
The test samples obtained in the examples and the comparative examples are subjected to continuous erosion wear test, and the method specifically comprises the following steps: and (3) continuously scouring and wearing the sample piece by using water drops with the flow rate of 1drop/s, wherein the sample piece forms an included angle of 60 degrees with the horizontal plane during scouring, and naturally drying the sample piece after continuously scouring for 48 hours. The photocatalytic performance of the sample piece was tested using the photocatalytic performance test conditions described above.
The stability test is carried out on the composite titanium dioxide photocatalytic concentrated solution obtained in each embodiment and comparative example, and the method specifically comprises the following steps: placing 500mL of the finished concentrated solution in a glass bottle (height 25cm and inner diameter 6cm) with the same size, standing for 1 day, 7 days and 30 days respectively, and observing the sedimentation condition of the product; then, stirring and redispersing each standing sample by using a cantilever stirrer at the rotating speed of 100r/min, and observing the redispersion condition of the sample; the photocatalytic performance of the redispersed product is tested again by the method, and the experimental results are shown in the following table 1.
TABLE 1
As can be seen from the data in Table 1, the titanium dioxide photocatalytic digestion membrane prepared from the composite titanium dioxide photocatalytic concentrated solution has good photocatalytic performance and wear resistance, and the concentrated solution system has strong stability and is not easy to generate sedimentation. Specifically, the difference between the comparative example 1 and the example 1 is that sodium alginate is replaced by hydroxyethyl cellulose in the comparative example 1, and the concentrated solution of the comparative example 1 is totally settled after 7 days, so that the system stability is poor; the difference between comparative example 2 and example 2 is that in comparative example 2, polyvinyl alcohol is used to replace sodium alginate, and the concentrated solution 1 of comparative example 2 is totally settled after the day, so that the system stability is poor. Examples 1 to 3 have better photocatalytic performance and abrasion resistance and better stability of the concentrated liquid system than examples 4 and 5, and are preferred embodiments.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The composite titanium dioxide photocatalytic concentrated solution is characterized by comprising the following preparation raw materials in percentage by mass:
5.0-50.0 percent of titanium dioxide nano particles, 5.0-30.0 percent of porous adsorbing material, 1.0-5.0 percent of sodium alginate, 10.0-50.0 percent of inorganic adhesive and the balance of water.
2. The compound titanium dioxide photocatalytic concentrated solution as set forth in claim 1, wherein the raw materials for preparation thereof comprise, in mass percent:
10.0-30.0 percent of titanium dioxide nano particles, 10.0-20.0 percent of porous adsorbing material, 1.0-3.0 percent of sodium alginate, 10.0-30.0 percent of inorganic adhesive and the balance of water.
3. The photocatalytic concentrated solution of composite titanium dioxide according to claim 1, characterized in that:
the titanium dioxide nano particles are a mixture of rutile type titanium dioxide and anatase type titanium dioxide, and the mass percent of the anatase type titanium dioxide is 70% -90%.
4. The composite titanium dioxide photocatalytic concentrated solution according to claim 1, characterized in that:
the particle size of the titanium dioxide nano-particles is 20-50 nm.
5. The photocatalytic concentrated solution of composite titanium dioxide according to claim 1, characterized in that:
the porous adsorption material is a material with micropores or mesopores, and the material is one or a mixture of more of silicate materials, aluminosilicate materials, porous carbon materials and metal-organic framework materials.
6. The composite titanium dioxide photocatalytic concentrated solution according to claim 5, characterized in that:
the particle fineness of the porous adsorption material is more than 300 meshes.
7. The photocatalytic concentrated solution of composite titanium dioxide according to claim 1, characterized in that:
the inorganic adhesive is one or a mixture of sodium silicate, solid sodium silicate and liquid sodium silicate.
8. A method for preparing the composite titanium dioxide photocatalytic concentrate according to any one of claims 1 to 7, characterized by comprising the steps of:
and mixing the preparation raw materials of the composite titanium dioxide photocatalytic concentrated solution to obtain the composite titanium dioxide photocatalytic concentrated solution.
9. A titanium dioxide photocatalytic digestion membrane is characterized by being prepared from the compound titanium dioxide photocatalytic concentrated solution as claimed in any one of claims 1 to 7.
10. A method of making the titanium dioxide photocatalytic digestion membrane according to claim 9, characterized by the steps of:
and (3) diluting the compound titanium dioxide photocatalytic concentrated solution, then coating the diluted compound titanium dioxide photocatalytic concentrated solution on the surface and drying to obtain the titanium dioxide photocatalytic digestion membrane.
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| CN114192133A (en) * | 2021-12-27 | 2022-03-18 | 中森美天(北京)环保科技有限责任公司 | Titanium dioxide photocatalytic stock solution, digestion membrane and preparation method thereof |
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