阅读说明：本技术 一种具有红外热效应的复合型有机气体污染物净化剂及其制备方法 (Composite organic gas pollutant purifying agent with infrared thermal effect and preparation method thereof ) 是由 付晓美 罗祎玮 陈柏存 梁静静 傅华康 毛水鑫 于 2021-06-30 设计创作，主要内容包括：本发明公开了一种具有红外热效应的复合型有机气体污染物净化剂,包含红外热效应/吸附催化剂,水性成膜剂,表面活性剂,保湿剂,分散剂和去离子水。将红外热效应/吸附催化剂与分散剂加入20℃-35℃的去离子水中,以200-500r/min的转速搅拌3-5h,待溶液呈均一稳定的悬浊液,再向混合液中加入保湿剂、表面活性剂、水性成膜剂,继续搅拌2-4h即可得有机气体污染物净化剂。它在低温下也能快速捕捉空气中以及室内家居表面的甲醛、苯、甲苯、二甲苯等有机气体污染物,并将其催化分解为二氧化碳和水,一年四季全天候对室内有机污染物都有快速持久的去除效果。(The invention discloses a compound organic gas pollutant purifying agent with infrared thermal effect, which comprises an infrared thermal effect/adsorption catalyst, a water-based film-forming agent, a surfactant, a humectant, a dispersing agent and deionized water. Adding the infrared thermal effect/adsorption catalyst and the dispersing agent into deionized water at the temperature of 20-35 ℃, stirring for 3-5 hours at the rotating speed of 200-500r/min until the solution is a uniform and stable suspension, adding the humectant, the surfactant and the aqueous film forming agent into the mixed solution, and continuously stirring for 2-4 hours to obtain the organic gas pollutant purifying agent. The catalyst can also quickly capture organic gas pollutants such as formaldehyde, benzene, toluene, xylene and the like in the air and on the surfaces of indoor households at low temperature, and catalytically decompose the organic gas pollutants into carbon dioxide and water, so that the catalyst has a quick and lasting effect on removing indoor organic pollutants all the year round.)

1. A composite organic gas pollutant purifying agent with infrared thermal effect is characterized in that: comprises an infrared thermal effect/adsorption catalyst, a water-based film forming agent, a surfactant, a humectant, a dispersant and deionized water.

2. The compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the concrete components are as follows according to mass fraction:

3. the compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the infrared thermal effect/adsorption catalyst is ATO-MnO₂A diatomite catalyst.

4. The compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the surfactant is one or a mixture of fatty alcohol-polyoxyethylene ether, sodium alkyl benzene sulfonate and succinic acid alkyl ester sodium sulfonate.

5. The compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the water-based film forming agent is degradable hydroxypropyl chitosan or chitosan quaternary ammonium salt.

6. The compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the dispersing agent is one or a mixture of xanthan gum, polydimethylsiloxane and hydroxypropyl methyl cellulose.

7. The compound organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 1, wherein: the humectant is one or a mixture of glycerol, urea and hydroxyethyl urea.

8. A preparation method of a compound organic gas pollutant purifying agent with infrared thermal effect as claimed in any one of claims 1 to 7, characterized in that: prepared ATO-MnO₂Grinding the diatomite catalyst with a ball mill, sieving with a 2500-mesh sieve, and sieving with a 2500-mesh sieve to obtain ATO-MnO₂Adding the diatomite catalyst and the dispersing agent into deionized water at the temperature of 20-35 ℃, stirring for 3-5 hours at the rotating speed of 200-500r/min until the solution is a uniform and stable suspension, adding the humectant, the surfactant and the aqueous film forming agent into the mixed solution, and continuing to add the humectant, the surfactant and the aqueous film forming agent into the mixed solutionStirring for 2-4h to obtain the organic gas pollutant purifying agent.

9. The preparation method of the composite organic gas pollutant purifying agent with infrared thermal effect as claimed in claim 8, wherein the preparation method comprises the following steps: the ATO-MnO₂The preparation method of the diatomite catalyst comprises the following steps:

(1) according to the mass ratio of the tin to the antimony as 5: 1-10: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 10-50mL of absolute ethanol, and adding 0.10g of tartaric acid to prepare a coating solution A;

(2) weighing 1-5g of urea for adjusting pH, adding 60-100mL of deionized water, magnetically stirring for dissolving, and adding 1-5g of MnO₂Mixing with 0.1-1g polyvinylpyrrolidone, stirring, and ultrasonic dispersing for 50-100min to obtain mixed slurry B;

(3) when the reaction temperature is 50-100 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continuously carried out for 5 hours at the temperature of 50-100 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the obtained precursor powder in air atmosphere at 500-650 ℃ for 2-3h to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the catalyst and the nano diatomite in distilled water, stirring uniformly, adding a citric acid complexing agent, adjusting the pH value to 5-7 by using ammonia water, heating to 70 ℃, drying at 105 ℃ until the mixture is in a wet gel state, and changing the wet gel into dry gel; the dried xerogel is placed in a muffle furnace to be calcined for 1-2h at the temperature of 500-650 ℃, then cooled to room temperature and ground to obtain ATO-MnO₂A diatomite catalyst.

Technical Field

The invention relates to the technical field of air purification, in particular to a composite organic gas pollutant purifying agent with infrared thermal effect and a preparation method thereof.

Background

Along with the improvement of the health consciousness of people, the requirements of people on indoor living environment are higher and higher, but in recent years, along with the rapid development of economy, the decoration of people on offices, living rooms and the like is more and more common, the requirements of the installation of equipment such as air conditioners, floor heating and the like on the air tightness of the space are higher and higher, the indoor and outdoor air exchange is less and less, and the pollution condition of organic pollutants is serious day by day. And organic volatile matters such as formaldehyde, benzene, toluene and the like have high toxicity, and indoor pollution becomes a healthy killer for human beings.

The gradual aggravation of the air quality problem forces people to accelerate the treatment of indoor air pollutants, and generally, the treatment is carried out by three ways: source control, ventilation dilution and air purification. The source control is mainly started from the characteristics of organic pollutants volatilized by materials, but due to lack of understanding of a micro mechanism level of the organic pollutants released by the materials, characteristic parameters influencing volatilization cannot be accurately measured, so that the volatilization characteristics of the materials cannot be reasonably predicted; although ventilation dilution is the simplest and convenient way for removing indoor organic pollutants, the effect of removing pollutants is very little because opening doors and windows for ventilation belongs to one of natural ventilation, the air quantity is small, the air speed is low; compared with source control and ventilation dilution, air purification is the method for removing indoor organic pollutants most quickly and effectively, and the removal mechanism is to remove the indoor organic pollutants in the modes of adsorption, catalysis, chemical reaction and the like.

The adsorption type air purifying agent has quick effect of removing organic pollutants, for example, the patent CN107252679A proposes that diatom and aluminum trioxide are used for removing indoor organic peculiar smell, but the adsorbent is easy to saturate and desorb, and the air purifying durability is poor. Chemical reaction type air purification has good effect of removing organic pollutant formaldehyde, and patents CN103127646B and CN108479346B propose that imidazolidone derivatives and amino acid are used for removing indoor formaldehyde, but the chemical reaction type air purification has poor effect of removing VOCs such as benzene, toluene and the like. The catalytic air purification has good catalytic decomposition effect on various organic pollutants such as formaldehyde, benzene, toluene, xylene and the like, has good air purification durability due to the self-cleaning characteristic, and is an ideal air purifying agent. The patent CN104624037B proposes that titanium dioxide is used as a photocatalyst to remove indoor organic pollutants, but the forbidden bandwidth of titanium dioxide is 3.2Ev, electrons need higher energy when jumping from a valence band to a conduction band, and only under the irradiation of ultraviolet light, the titanium dioxide has a catalytic effect, and under the natural illumination, the titanium dioxide has a very small effect of catalyzing the organic pollutants; patent CN111036071A proposes the use of thermal catalyst active manganese to remove organic pollutants in air, and the catalytic action of active manganese needs a certain amount of heat energy to drive although no light is needed, and the catalytic rate is low under low temperature condition, especially in winter.

Disclosure of Invention

The invention aims to provide a composite organic gas pollutant purifying agent with infrared thermal effect and a preparation method thereof, which can quickly capture organic gas pollutants such as formaldehyde, benzene, toluene, xylene and the like in the air and on the surface of indoor home at low temperature and catalytically decompose the organic gas pollutants into carbon dioxide and water, and has quick and lasting removing effect on the indoor organic pollutants all the year round.

In order to solve the technical problems, the invention adopts the following technical scheme:

a composite organic gas pollutant purifying agent with infrared thermal effect comprises an infrared thermal effect/adsorption catalyst, a water-based film-forming agent, a surfactant, a humectant, a dispersing agent and deionized water.

The infrared thermal effect/adsorption catalyst absorbs infrared light to heat the substrate, so that the catalytic activity of the catalyst can be improved under the drive of heat energy, the volatilization of organic pollutants on the surface of a household contacted with the catalyst can be accelerated, and the catalyst has an excellent removal effect on organic gas pollutants at low temperature and in the absence of light.

Preferably, the specific components are as follows in mass fraction:

preferably, the infrared thermal effect/adsorption catalyst is ATO-MnO₂A diatomite catalyst. Wherein MnO is₂The catalyst is a thermal catalyst, and can play a role of catalysis only under the drive of certain heat energy. ATO (antimony tin oxide) is an excellent infrared absorber, whose absorption of infrared light raises the temperature of its substrate. Modifying MnO with ATO₂Preparation of ATO-MnO with infrared thermal catalytic effect₂ATO-MnO thereof₂Has excellent catalytic performance. Then adding ATO-MnO₂Preparation of ATO-MnO from diatomite with porous structure₂A diatomite catalyst which actively adsorbs organic pollutant molecules in the air and rapidly decomposes the pollutant molecules into carbon dioxide and water.

Preferably, the surfactant is one or a mixture of fatty alcohol-polyoxyethylene ether, sodium alkyl benzene sulfonate and sodium alkyl sulfosuccinate. The surfactant is used for reducing the contact angle between the purifying agent and the surface of an object capable of releasing organic gas pollutants when the purifying agent is sprayed on the surface of the object, so that the purifying agent is completely soaked and covers the surface of the sprayed object.

Preferably, the aqueous film forming agent is one of degradable hydroxypropyl chitosan or chitosan quaternary ammonium salt.

Preferably, the dispersing agent is one of xanthan gum, polydimethylsiloxane and hydroxypropyl methylcellulose or a mixture thereof. Such dispersants enable ATO-MnO₂The diatomite catalyst is uniformly dispersed in the spray aqueous system.

Preferably, the humectant is one or a mixture of glycerol, urea and hydroxyethyl urea.

A kind of utensilThe preparation method of the compound organic gas pollutant purifying agent with the infrared thermal effect comprises the following steps: prepared ATO-MnO₂Grinding the diatomite catalyst with a ball mill, sieving with a 2500-mesh sieve, and sieving with a 2500-mesh sieve to obtain ATO-MnO₂Adding the diatomite catalyst and the dispersing agent into deionized water at the temperature of 20-35 ℃, stirring for 3-5 hours at the rotating speed of 200-500r/min until the solution is a uniform and stable suspension, adding the humectant, the surfactant and the aqueous film forming agent into the mixed solution, and continuously stirring for 2-4 hours to obtain the organic gas pollutant purifying agent.

Preferably, ATO-MnO₂The preparation method of the diatomite catalyst comprises the following steps:

(1) according to the mass ratio of the tin to the antimony as 5: 1-10: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 10-50mL of absolute ethanol, and adding 0.10g of tartaric acid to prepare a coating solution A;

(2) weighing 1-5g of urea for adjusting pH, adding 60-100mL of deionized water, magnetically stirring for dissolving, and adding 1-5g of MnO₂Mixing with 0.1-1g polyvinylpyrrolidone, stirring, and ultrasonic dispersing for 50-100min to obtain mixed slurry B;

(3) when the reaction temperature is 50-100 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continuously carried out for 5 hours at the temperature of 50-100 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the obtained precursor powder in air atmosphere at 500-650 ℃ for 2-3h to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the catalyst and the nano diatomite in distilled water, stirring uniformly, adding a citric acid complexing agent, adjusting the pH value to 5-7 by using ammonia water, heating to 70 ℃, drying at 105 ℃ until the mixture is in a wet gel state, and changing the wet gel into dry gel; the dried xerogel is placed in a muffle furnace to be calcined for 1-2h at the temperature of 500-650 ℃, then cooled to room temperature and ground to obtain ATO-MnO₂A diatomite catalyst.

Due to the adoption of the technical scheme, the invention has the following beneficial effects:

(1) the organic gas pollutant purifying agent provided by the invention contains ATO-MnO₂The diatomite catalyst is used for absorbing infrared light in the environment by ATO when the purifying agent is sprayed on the surface of a home, so that the MnO of the substrate is MnO₂Heating up diatomite and improving MnO under the drive of heat energy₂The catalytic activity of the composite material can accelerate the volatilization of organic pollutants on the surface of the household contacted with the composite material, and the composite material has excellent removal effect on organic gas pollutants at low temperature and in no light.

(2) After the organic gas pollutant purifying agent provided by the invention is sprayed on the surface of a home, an adsorption system with a pore structure can quickly capture free organic gas pollutants such as formaldehyde, benzene, toluene and the like on the surface of furniture and in the air, and then the pollutants are catalytically decomposed on the surface of a catalytic system, so that indoor organic gas pollutants can be quickly removed; meanwhile, due to the self-cleaning property of the catalyst, the catalyst can not be consumed when reacting with organic pollutants, and has excellent durability on the removal of the organic gas pollutants.

(3) The organic gas pollutant purifying agent provided by the invention contains the film-forming agent modified chitosan, amino groups on the molecular structure of the modified chitosan can react with formaldehyde pollutants in the air, and when the modified chitosan is sprayed on the household surface, the formed water-based film can decompose the formaldehyde pollutants and has a barrier effect on the volatile organic gas pollutants on the household surface.

(4) The organic gas pollutant purifying agent provided by the invention contains an infrared thermal effect/adsorption catalyst and a water-based film forming agent. After the spray is sprayed on the household surface, when organic gas pollutants volatilize from furniture, most organic pollutant molecules are immediately and uniformly dispersed in the infrared heat effect/adsorption catalyst in the closed membrane to be directly adsorbed and decomposed, so that the decomposed pollutants are not likely to collide with the infrared heat effect/adsorption catalyst again in a form of free molecular diffusion due to being blocked by the closed membrane, and are finally completely decomposed. The existence of the closed membrane increases the opportunity that the organic gas pollutants are contacted with the surface of the infrared thermal effect/adsorption catalyst, and the volatile organic gas pollutants in the house can be thoroughly removed.

Drawings

The invention is further illustrated below with reference to the accompanying drawings.

FIG. 1 is a graph of formaldehyde removal rate for 24h at 6. + -. 2 ℃ for example 8 and comparative examples 1-2.

Detailed Description

The present invention is further illustrated by the following examples.

Example 1

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of the tin to the antimony as 5: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) 1g of urea is weighed to adjust the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 1.0 part of ATO-MnO passed through the 2500 mesh sieve₂Diatomite catalyst and 1.0 part of xanthan gumAdding 100 parts of deionized water at 25 ℃, stirring at the rotating speed of 400r/min for 4 hours until the solution is a uniform and stable suspension, adding 0.2 part of hydroxyethyl urea, 0.5 part of fatty alcohol-polyoxyethylene ether and 1.5 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 2

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of tin to antimony being 7: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) weighing 2g of urea for adjusting pH, adding 75mL of deionized water, magnetically stirring for dissolving, and adding 1.8g of MnO₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 1.0 part of ATO-MnO passed through the 2500 mesh sieve₂Adding diatomite catalyst and 1.0 part of xanthan gum into 100 parts of deionized water at 25 ℃, stirring at the rotating speed of 400r/min for 4 hours until the solution is uniformAdding 0.2 part of hydroxyethyl urea, 0.5 part of fatty alcohol-polyoxyethylene ether and 1.5 parts of degradable hydroxypropyl chitosan into the mixed solution after the suspension is stabilized, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 3

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of tin to antimony of 10: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) 5g of urea is weighed for adjusting the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 1.0 part of ATO-MnO passed through the 2500 mesh sieve₂Adding diatomite catalyst and 1.0 part of xanthan gum into 100 parts of deionized water at 25 ℃, stirring at the rotating speed of 400r/min for 4 hours until the solution is uniform and stable suspension, and adding 0.2 part of hydroxyethyl urea and 0.5 part of grease into the mixed solutionAnd (3) continuously stirring fatty alcohol polyoxyethylene ether and 1.5 parts of degradable hydroxypropyl chitosan for 4 hours to obtain the organic gas pollutant purifying agent.

Example 4

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of the tin to the antimony as 5: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) 1g of urea is weighed to adjust the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 3.0 parts of ATO-MnO passed through the 2500 mesh sieve₂Adding diatomite catalyst and 3.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is uniform and stable suspension, adding 0.5 part of hydroxyethyl urea, 1.0 part of fatty alcohol-polyoxyethylene ether and 3.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hoursAnd obtaining the organic gas pollutant purifying agent.

Example 5

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of tin to antimony being 7: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) weighing 2g of urea for adjusting pH, adding 75mL of deionized water, magnetically stirring for dissolving, and adding 1.8g of MnO₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) ATO-MnO prepared as above₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 3.0 parts of ATO-MnO passed through the 2500 mesh sieve₂Adding a diatomite catalyst and 3.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is uniform and stable suspension, adding 0.5 part of hydroxyethyl urea, 1.0 part of fatty alcohol-polyoxyethylene ether and 3.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 6

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of tin to antimony of 10: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) 5g of urea is weighed for adjusting the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) ATO-MnO prepared as above₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 3.0 parts of ATO-MnO passed through the 2500 mesh sieve₂Adding a diatomite catalyst and 3.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is uniform and stable suspension, adding 0.5 part of hydroxyethyl urea, 1.0 part of fatty alcohol-polyoxyethylene ether and 3.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 7

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of the tin to the antimony as 5: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) 1g of urea is weighed to adjust the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 5.0 parts of ATO-MnO through the 2500 mesh sieve₂Adding a diatomite catalyst and 5.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is a uniform and stable suspension, adding 1.0 part of hydroxyethyl urea, 2.0 parts of fatty alcohol-polyoxyethylene ether and 5.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 8

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) based on tin-antimony substancesThe quantity ratio is 7: 1 separately weighing SnCl₄·5H₂O and SbCl₃Dissolving in 35mL of absolute ethyl alcohol, and then adding 0.10g of tartaric acid to prepare a coating solution A;

(2) weighing 2g of urea for adjusting pH, adding 75mL of deionized water, magnetically stirring for dissolving, and adding 1.8g of MnO₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 5.0 parts of ATO-MnO through the 2500 mesh sieve₂Adding a diatomite catalyst and 5.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is a uniform and stable suspension, adding 1.0 part of hydroxyethyl urea, 2.0 parts of fatty alcohol-polyoxyethylene ether and 5.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Example 9

Preparing a compound organic gas pollutant purifying agent with infrared thermal effect:

(1) according to the mass ratio of tin to antimony of 10: 1 separately weighing SnCl₄·5H₂O and SbCl₃DissolutionAdding 0.10g of tartaric acid into 35mL of absolute ethanol to prepare a coating solution A;

(2) 5g of urea is weighed for adjusting the pH value, 75mL of deionized water is added, the mixture is dissolved by magnetic stirring, and 1.8g of MnO is added₂Mixing with 0.21g polyvinylpyrrolidone, stirring, ultrasonic dispersing for 60min to obtain mixed slurry B;

(3) when the reaction temperature is 80 ℃, the coating liquid A is dropwise added into the mixed slurry B at the speed of 0.4r/min by a peristaltic pump, and after the dropwise addition is finished, the condensation and reflux are continued for 5 hours at the temperature of 90 ℃;

(4) standing and cooling the precursor slurry obtained by the reaction for 3h, filtering, washing, drying in vacuum at 60 ℃ for 5h, grinding, calcining the precursor powder at 600 ℃ for 2h in air atmosphere to obtain ATO-MnO₂A catalyst;

(5) prepared ATO-MnO₂Dispersing the mixture and nano diatomite by using distilled water, uniformly stirring, adding a citric acid complexing agent, adjusting the pH value to 6 by using ammonia water, then heating to 70 ℃, and drying at 105 ℃ until the wet gel is changed into dry gel after the mixture is in the wet gel state; calcining the dried xerogel in a muffle furnace at 650 ℃ for 1-2h, cooling to room temperature, and grinding to obtain ATO-MnO₂A diatomite catalyst.

(6) Prepared ATO-MnO₂Grinding the diatomaceous earth catalyst with a ball mill, sieving with a 2500 mesh sieve, and then passing 5.0 parts of ATO-MnO through the 2500 mesh sieve₂Adding a diatomite catalyst and 5.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is a uniform and stable suspension, adding 1.0 part of hydroxyethyl urea, 2.0 parts of fatty alcohol-polyoxyethylene ether and 5.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Comparative example 1

Preparing an organic gas pollutant purifying agent:

firstly, adding 5.0 parts of diatomite and 5.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is a uniform and stable suspension, then adding 1.0 part of hydroxyethyl urea, 12.0 parts of fatty alcohol-polyoxyethylene ether and 5.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Comparative example 2

Preparing an organic gas pollutant purifying agent:

first, 5.0 parts of MnO₂Adding 5.0 parts of xanthan gum into 100 parts of deionized water at 25 ℃, stirring for 4 hours at the rotating speed of 400r/min until the solution is uniform and stable suspension, adding 1.0 part of hydroxyethyl urea, 2.0 parts of fatty alcohol-polyoxyethylene ether and 5.0 parts of degradable hydroxypropyl chitosan into the mixed solution, and continuously stirring for 4 hours to obtain the organic gas pollutant purifying agent.

Performance index test of the organic gas contaminant purifiers described in examples 1 to 9 and comparative examples 1 to 2.

Sample state: examples 1 to 9 and comparative examples 1 to 2, each 100ml

The detection device comprises: shimadzu ultraviolet visible spectrophotometer and thermal desorption instrument-GC-MS combined instrument

Detection standard: QB/T2761-2006 method for determining purification effect of indoor air purification product

Sample preparation: the organic gas contaminant purification agent described in examples 1-3 and comparative examples 1-2 was sprayed three times on three square meter 1 square substrates (requiring inert materials). The spraying agent is sprayed for the first time and dried in the air and then for the second time, and then for the third time after the second time and dried in the air, wherein the spraying amount of the purifying agent is 100 ml.

The test conditions are as follows: two air experiment chambers (A is a blank chamber, and B is a sample chamber) are used for testing the concentration of the purified product for removing gas pollutants, and the experiment is carried out at a certain temperature and under normal pressure. The experiment chamber is clean and pollution-free.

Release source preparation:

winding 5 layers of 17cm x40cm medical absorbent gauze on 2 glass rods with diameter of 5mm and length of 30cm, fixing with cotton thread, vertically placing in 500ml reagent bottles, and filling 200ml of contaminants, wherein the concentrations are respectively 0.2% of formaldehyde, 1% of ammonia, 0.06% of benzene, 0.1% of toluene and 0.4% of xylene; the TVOC is prepared according to the specified proportion of benzene, toluene and xylene, and each reagent is analytically pure. The container is stuck with marks A1 and B1, and can be put into use after the gauze is completely wetted.

Experimental procedure

1) Suspending untreated base paper in a blank experiment cabin A, and suspending the untreated base paper in a test cabin B through base paper sprayed with a purifying material;

2) containers to be equipped with the prepared pollutant release sources a1 and B1 were placed in the blank test chamber a and the sample test chamber B, respectively, and the doors were immediately closed.

3) Starting fans of the blank test chamber A and the sample test chamber B, stirring for 1min to uniformly mix air in the chambers with pollutants released by the release sources, simultaneously closing the fans, sampling air in the blank chambers, and determining the concentration value of the pollutants in the air in the blank chambers as an initial concentration and marking the initial concentration as C₀。

4) After 24h, sampling the concentration of air pollutants in the two cabins, analyzing and testing to obtain a concentration value in A, B cabin within a certain period of time, and recording the concentration value as C_AAnd C_B。

5) The sampling method comprises the following steps: sampling and analysis of formaldehyde was carried out according to the regulations in GB/T18883; benzene, toluene, TVOC were sampled with a TENAX tube at a sampling rate of 200 ml/min.

6) And (3) calculating: calculation of the pollutant removal rate by the purifying agent:

in the formula:

y-removal rate%

C_A-concentration of contaminants in the blank test chamber in mg/m³

C_B-concentration of contamination in the real sample test chamber, mg/m³

The test results are shown in table 1.

Table 1: removal rate of organic gas pollutants at 20 +/-2 ℃ under normal pressure

By comparison, it can be seen that the ATO-MnO containing compounds of examples 1 to 9 were used at 20. + -. 2 ℃ under normal pressure₂The purifying spray of the diatomite catalyst has better purifying effect on organic gas pollutants than the comparative example 1 containing the adsorption diatomite and the non-modified MnO₂Comparative example 2. Among them, the purification spray prepared in example 8 has the best purification effect on organic gas pollutants.

As shown in FIG. 1, the purifiers prepared in example 8 of the present invention and comparative examples 1 and 2 were compared in the purification rate of formaldehyde and the removal rate of formaldehyde at a low temperature of 6. + -. 2 ℃ and the purifiers prepared in example 8 of the present invention had a faster removal rate and a higher removal rate of formaldehyde than the purifiers prepared in comparative examples 1 and 2 under the same ratio of the remaining components.

The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.