CN110256893B - Coating additive for guardrail capable of assisting in purifying automobile exhaust and preparation method thereof - Google Patents
Coating additive for guardrail capable of assisting in purifying automobile exhaust and preparation method thereof Download PDFInfo
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- CN110256893B CN110256893B CN201910524317.8A CN201910524317A CN110256893B CN 110256893 B CN110256893 B CN 110256893B CN 201910524317 A CN201910524317 A CN 201910524317A CN 110256893 B CN110256893 B CN 110256893B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention discloses the technical field of road materials, relates to the field of road guardrail coatings, and particularly relates to a coating additive for a road guardrail, which can assist in purifying automobile exhaust. The method comprises the steps of taking waste shells as raw materials, calcining, micro-etching and dispersing to obtain micron porous shell powder sol, and matching with nano titanium dioxide to obtain nano titanium dioxide modified micron porous shell powder gel particles. The nano titanium dioxide adsorbed on the surface has a photocatalysis effect, and is also nano anion powder commonly used in the coating, and the micron porous shell powder in the coating has a good adsorption effect. The coating is applied to the coating of the highway guardrail, so that the photocatalysis effect of the coating can be increased, the organic matters adsorbed on the surface of the coating can be degraded, and meanwhile, the adsorption effect of the surface of the coating on pollutants in the air can be increased, and the purification effect of nano anion powder in the coating on the air can be further enhanced.
Description
Technical Field
The invention belongs to the technical field of road materials, relates to the field of coatings for highway guardrails, and particularly relates to a coating additive for a highway guardrail, which can assist in purifying automobile exhaust.
Background
With the development of the tourism industry in recent years, self-driving tour has become a trend which is increasingly popular. However, the following travel safety is also receiving much attention, and particularly, traffic accidents caused by fatigue driving and the like are always on the eye in highway self-driving. Warning paint is usually applied to the guardrails of the road to remind and guide the driver to drive safely. Due to the requirements of the specific application environment of the coating for the guardrail of the highway, the coating needs to meet the corresponding performance.
The automobile on the highway discharges a large amount of tail gas, the main components of the automobile tail gas are solid suspended particles, carbon monoxide, hydrocarbon, oxynitride, sulfur dioxide and the like which are pollutants, and therefore, the coating for the highway guardrail has the potential requirement of being capable of purifying the tail gas of the automobile.
At present, the coating with the air purification function is usually added with nanometer negative ion components, and materials capable of continuously releasing negative ions are added into the coating to enable the coating to release the negative ions for a long time so as to decompose harmful gases in the air. However, such paint is generally applied to indoor environment, air flow is relatively slow, and for highway environment with extremely fast air flow, negative ions released from the paint are easy to diffuse into other environments along with wind, and the paint has the defect that a large amount of automobile exhaust gas existing in the highway pavement and the environment nearby the highway pavement cannot be effectively purified.
In order to purify automobile exhaust, a three-way catalyst is generally mounted on an automobile to purify carbon monoxide, hydrocarbons and nitrogen oxides in the automobile exhaust. The three-way catalyst mainly has the catalytic action, the catalyst usually adopts precious metals such as platinum, rhodium, palladium and the like, and takes alumina cotton fiber felt as a carrier to oxidize carbon monoxide into carbon dioxide, oxidize hydrocarbon into water and carbon dioxide and reduce oxynitride into nitrogen and oxygen at high temperature. However, the noble metals such as platinum, rhodium and palladium as catalysts are expensive and are still feasible for use in automobiles, and if they are used as additives of paints for facilities such as road barriers, the cost is too high. Therefore, it is necessary to develop an additive composition capable of catalyzing and purifying automobile exhaust gas, which can be widely applied to a coating material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a coating additive for a road guardrail, which can assist in purifying automobile exhaust.
The preparation method of the nanometer titanium dioxide-micron porous shell powder gel particles comprises the following steps:
preparation of one-micron porous shell powder sol
(1) Preparation of primary shell powder: grinding the shell, fully grinding, sieving by a 300-mesh sieve to obtain micron-sized shell powder, calcining for 5-20 minutes at the temperature of 300-450 ℃ in an aerobic environment, removing chitin in the shell powder, and preparing primary shell powder for later use. The chitin in the shell powder can be effectively removed by moderate-temperature calcination in an aerobic environment, and the calcium carbonate can be decomposed and is undesirable due to overhigh calcination temperature; the calcination temperature is too low, and there is a defect that the chitin cannot be effectively removed.
(2) Wet grinding: wet grinding the primary shell powder prepared in the step (1), and ball-milling for 1h in a ball-milling tank, wherein the shell powder and ethanol are mixed according to a ratio of 100 g: mixing at a ratio of 50-100ml, and wet grinding aid is ethanol. And the wet grinding is further carried out after the calcination, so that the agglomeration phenomenon of powder caused by the calcination can be effectively reduced, and the particle size of the shell powder is maintained at the micron level and is uniform.
(3) Preparing a slightly corrosive dispersing solvent: dissolving acetic acid in ethanol solution, and stirring to obtain slightly corrosive dispersing solvent with volume percentage of acetic acid and ethanol of 1-3%.
(4) And (3) dispersing 100g of the shell powder subjected to wet grinding in the step (2) and an auxiliary agent ethanol into 1L of the slightly corrosive dispersion solvent prepared in the step (3), and stirring for 1-3h by adopting a magnetic stirrer to prepare the micron porous shell powder sol. Acetic acid in the micro-corrosive dispersing solvent can slightly corrode the shell powder, so that corrosion pits are formed on the surface of the shell powder, the shell powder with a porous structure is obtained, and the adsorption effect of the shell powder can be improved. The use of too much acetic acid can dissolve a large amount of shell powder, and the use of too little acetic acid has the defect that an effective porous structure cannot be obtained.
Preparation of nano titanium dioxide sol
Mixing titanate with an ethanol solvent with the pH of 3-5 to prepare nano titanium dioxide sol, mixing the titanate and the ethanol according to the volume ratio of 1:10, adjusting the pH to 3-5 by using acetic acid, and continuously mechanically stirring for 2-4h to obtain the nano titanium dioxide sol.
Preparation of nano titanium dioxide-micron porous shell powder gel particles
Mixing the prepared micron porous shell powder sol and the nano titanium dioxide sol in a volume ratio of 3-5:1, and aging at room temperature for 5-10h to obtain the nano titanium dioxide-micron porous shell powder gel particles.
In the prepared nano titanium dioxide-micron porous shell powder gel particles, a large amount of nano titanium dioxide is adsorbed on the surface of a skeleton of a porous structure, and a small amount of nano titanium dioxide is adsorbed in holes of the porous structure, so that the adsorption effect of the porous shell powder is not influenced.
The chitin in the shell powder can be effectively removed by moderate-temperature calcination in an aerobic environment, and the calcium carbonate is decomposed and is undesirable due to overhigh calcination temperature; the calcination temperature is too low, and there is a defect that the chitin cannot be effectively removed. And the wet grinding is further carried out after the calcination, so that the agglomeration phenomenon of powder caused by the calcination can be effectively reduced, and the particle size of the shell powder is maintained at the micron level and is uniform. The auxiliary agent used in the wet grinding and the solvent in the sol preparation process are both ethanol, so that the shell powder after the wet grinding and the auxiliary agent ethanol can be directly dispersed into a slightly corrosive dispersing solvent. A proper amount of acetic acid is added into the micro-corrosive dispersing solvent, and the acetic acid can slightly corrode calcium carbonate, so that part of pits are formed on the surface of the shell powder, and the shell powder with a porous structure is obtained. The porous structure can enhance the adsorption effect of the shell powder. The use of too much acetic acid can dissolve a large amount of shell powder, and the use of too little acetic acid has the defect that an effective porous structure cannot be obtained. In addition, if strong acids such as hydrochloric acid and nitric acid are used, there are cases where the acidity is too strong to cause dissolution of a large amount of shell powder. In the process of preparing the titanium dioxide sol, ethanol is also used as a solvent, and continuous mechanical stirring is matched to ensure that the nano titanium dioxide sol is obtained. Mixing the micron porous shell powder sol which is 3-5 times of the nanometer titanium dioxide sol with the nanometer titanium dioxide sol, so that a large amount of the nanometer titanium dioxide is adsorbed on the surface of a skeleton of a porous structure, a small amount of the nanometer titanium dioxide is adsorbed in holes of the porous structure, and the adsorption effect of the porous shell powder is not affected. The nano titanium dioxide adsorbed on the surface has a photocatalysis effect, and is also nano anion powder commonly used in the coating, and the micron porous shell powder in the coating has a good adsorption effect. Therefore, the prepared nano titanium dioxide-micron porous shell powder gel particles are applied to the highway guardrail coating, so that the photocatalysis effect of the coating can be increased, organic matters adsorbed on the surface of the coating can be degraded, and meanwhile, the adsorption effect of the surface of the coating on pollutants in the air can be increased, so that the air pollutants are gathered in the radiation range of nano negative ions, and the purification effect of the nano negative ion powder in the coating on the air is further enhanced.
Detailed Description
Example 1
The preparation method of the nanometer titanium dioxide-micron porous shell powder gel particles comprises the following steps:
preparation of one-micron porous shell powder sol
(1) Preparation of primary shell powder: grinding the shell, fully grinding, sieving by a 300-mesh sieve to obtain micron-sized shell powder, calcining for 20 minutes at 300 ℃ in an aerobic environment, removing chitin in the shell powder, and preparing primary shell powder for later use;
(2) wet grinding: wet grinding the primary shell powder prepared in the step (1), and ball-milling for 1h in a ball-milling tank, wherein the shell powder and ethanol are mixed according to a ratio of 100 g: 100ml of the mixture is mixed, and the wet grinding auxiliary agent is ethanol;
(3) preparing a slightly corrosive dispersing solvent: dissolving acetic acid in an ethanol solution, and fully and uniformly stirring to prepare a slightly corrosive dispersion solvent, wherein the volume percentage of the acetic acid to the ethanol is 3%;
(4) dispersing 100g of the shell powder subjected to wet grinding in the step (2) and an auxiliary agent ethanol into 1L of the slightly corrosive dispersion solvent prepared in the step (3), and stirring for 3h by adopting a magnetic stirrer to prepare a micron porous shell powder sol;
preparation of nano titanium dioxide sol
Mixing titanate with an ethanol solvent with the pH value of 5 to prepare nano titanium dioxide sol, mixing the titanate and the ethanol according to the volume ratio of 1:10, adjusting the pH value to 5 by using acetic acid, and continuously mechanically stirring for 4 hours to obtain the nano titanium dioxide sol;
preparation of nano titanium dioxide-micron porous shell powder gel particles
Mixing the prepared micron porous shell powder sol and the nano titanium dioxide sol in a volume ratio of 5:1, and aging at room temperature for 10h to obtain the nano titanium dioxide-micron porous shell powder gel particles.
Example 2
The preparation method of the nanometer titanium dioxide-micron porous shell powder gel particles comprises the following steps:
preparation of one-micron porous shell powder sol
(1) Preparation of primary shell powder: grinding the shell, fully grinding, sieving by a 300-mesh sieve to obtain micron-sized shell powder, calcining for 10 minutes at 400 ℃ in an aerobic environment, removing chitin in the shell powder, and preparing primary shell powder for later use;
(2) wet grinding: wet grinding the primary shell powder prepared in the step (1), and ball-milling for 1h in a ball-milling tank, wherein the shell powder and ethanol are mixed according to a ratio of 100 g: 80ml of the mixture is mixed, and the wet grinding auxiliary agent is ethanol;
(3) preparing a slightly corrosive dispersing solvent: dissolving acetic acid in an ethanol solution, and fully and uniformly stirring to prepare a slightly corrosive dispersion solvent, wherein the volume percentage of the acetic acid to the ethanol is 2%;
(4) dispersing 100g of the shell powder subjected to wet grinding in the step (2) and an auxiliary agent ethanol into 1L of the slightly corrosive dispersion solvent prepared in the step (3), and stirring for 2h by adopting a magnetic stirrer to prepare micron porous shell powder sol;
preparation of nano titanium dioxide sol
Mixing titanate with an ethanol solvent with the pH value of 4 to prepare nano titanium dioxide sol, mixing the titanate and the ethanol according to the volume ratio of 1:10, adjusting the pH value to 4 by using acetic acid, and continuously mechanically stirring for 3 hours to obtain the nano titanium dioxide sol;
preparation of nano titanium dioxide-micron porous shell powder gel particles
Mixing the prepared micron porous shell powder sol and the nano titanium dioxide sol in a volume ratio of 4:1, and aging at room temperature for 8 hours to obtain the nano titanium dioxide-micron porous shell powder gel particles.
Example 3
The preparation method of the nanometer titanium dioxide-micron porous shell powder gel particles comprises the following steps:
preparation of one-micron porous shell powder sol
(1) Preparation of primary shell powder: grinding the shell, fully grinding, sieving by a 300-mesh sieve to obtain micron-sized shell powder, calcining for 5 minutes at 450 ℃ in an aerobic environment, removing chitin in the shell powder, and preparing primary shell powder for later use;
(2) wet grinding: wet grinding the primary shell powder prepared in the step (1), and ball-milling for 1h in a ball-milling tank, wherein the shell powder and ethanol are mixed according to a ratio of 100 g: mixing at a ratio of 50ml, and wet grinding aid is ethanol;
(3) preparing a slightly corrosive dispersing solvent: dissolving acetic acid in an ethanol solution, and fully and uniformly stirring to prepare the slightly corrosive dispersion solvent, wherein the volume percentage of the acetic acid to the ethanol is 1%.
(4) Dispersing 100g of the shell powder subjected to wet grinding in the step (2) and an auxiliary agent ethanol into 1L of the slightly corrosive dispersion solvent prepared in the step (3), and stirring for 1h by adopting a magnetic stirrer to prepare a micron porous shell powder sol;
preparation of nano titanium dioxide sol
Mixing titanate with an ethanol solvent with the pH value of 3 to prepare nano titanium dioxide sol, mixing the titanate and the ethanol according to the volume ratio of 1:10, adjusting the pH value to 3 by using acetic acid, and continuously mechanically stirring for 2 hours to obtain the nano titanium dioxide sol.
Preparation of nano titanium dioxide-micron porous shell powder gel particles
Mixing the prepared micron porous shell powder sol and the nano titanium dioxide sol in a volume ratio of 3:1, and aging at room temperature for 5 hours to obtain the nano titanium dioxide-micron porous shell powder gel particles.
Comparative example
Common nano titanium dioxide anion additives are used for comparison.
The coating additives of examples 1-3 were added to the coating, and compared with the coating additives added with a common nano titanium dioxide anion additive, the cleaning effect of each coating on automobile exhaust in a closed space and a flowing space was compared, respectively. After 48 hours of simulation, the results are shown in Table 1.
TABLE 1 decontamination Effect test of coatings with the addition of coating additives of examples 1-3 and comparative examples
| Purification ratio of closed space (%) | Purification ratio of flow space (%) | |
| Example 1 | 89 | 85 |
| Example 2 | 87 | 84 |
| Example 3 | 88 | 84 |
| Comparative example | 85 | 60 |
As can be seen from the results of comparing examples 1 to 3 with the comparative example, the coating additive of the present invention can significantly improve the air-purifying effect of the coating in the flow space. The nano titanium dioxide-micron porous shell powder gel particles adopted in the coating additive can increase the adsorption effect of the coating surface on pollutants in the air, so that the air pollutants are gathered in the radiation range of nano negative ions, the purification effect of the nano negative ion powder in the coating on the air is further enhanced, and the nano titanium dioxide-micron porous shell powder gel particles and the nano negative ion powder have obvious synergistic gain effect.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.
Claims (1)
1. The preparation method of the paint additive for the road guardrail capable of assisting in purifying the automobile exhaust comprises the following steps of:
preparation of one-micron porous shell powder sol
(1) Preparation of primary shell powder: grinding the shell, fully grinding, sieving by a 300-mesh sieve to obtain micron-sized shell powder, calcining for 5-20 minutes at the temperature of 300-450 ℃ in an aerobic environment, removing chitin in the shell powder, and preparing primary shell powder for later use;
(2) wet grinding: wet grinding the primary shell powder prepared in the step (1), and ball-milling for 1h in a ball-milling tank, wherein the shell powder and ethanol are mixed according to a ratio of 100 g: mixing at a ratio of 50-100ml, and wet grinding aid is ethanol;
(3) preparing a slightly corrosive dispersing solvent: dissolving acetic acid in an ethanol solution, and fully and uniformly stirring to prepare a slightly corrosive dispersion solvent, wherein the volume percentage of the acetic acid to the ethanol is 1-3%;
(4) dispersing 100g of the shell powder subjected to wet grinding in the step (2) and an auxiliary agent ethanol into 1L of the slightly corrosive dispersion solvent prepared in the step (3), and stirring for 1-3h by adopting a magnetic stirrer to prepare micron porous shell powder sol;
preparation of nano titanium dioxide sol
Mixing titanate with an ethanol solvent with the pH of 3-5 to prepare nano titanium dioxide sol, mixing the titanate and the ethanol according to the volume ratio of 1:10, adjusting the pH to 3-5 by using acetic acid, and continuously mechanically stirring for 2-4h to obtain the nano titanium dioxide sol;
preparation of nano titanium dioxide-micron porous shell powder gel particles
Mixing the prepared micron porous shell powder sol and the nano titanium dioxide sol in a volume ratio of 3-5:1, and aging at room temperature for 5-10h to obtain the nano titanium dioxide-micron porous shell powder gel particles.
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