CN107875778B - Nano zero-valent iron bubble and application thereof - Google Patents
Nano zero-valent iron bubble and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of environmental protection, and discloses a nano zero-valent iron bubble and application thereof. The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 60-80 parts of water, 8-12 parts of nano iron suspension, 4-7 parts of sodium polyacrylate, 3-5 parts of cocamidopropyl amine oxide, 1-2 parts of white vinegar, 1-3 parts of kason, 2-4 parts of glycerol and 3-7 parts of modified methyl cellulose. The nano zero-valent iron bubbles can remove large-area haze particulate matters in the air.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a nano zero-valent iron bubble for removing and washing haze in air.
Background
Haze is the result of specific climatic conditions interacting with human activity. Society and production activities of high-density population can discharge a large amount of fine particulate matters PM2.5 and harmful chemical gases into the air, wherein the large amount of fine particulate matters and harmful chemical gases exceed the atmospheric circulation capacity and the load bearing capacity, and when discharged gas pollutants form secondary particulate matters to contribute to the PM2.5, the concentration of the fine particulate matters is continuously accumulated. At this time, if affected by quiet weather and the like, the haze in a large range is easy to appear. Haze also contains a large amount of toxins such as carbon monoxide, carbon dioxide, hydrocarbons, organic nitrogen compounds, sulfur dioxide, and the like. Generally, people can add salt, baking soda, white vinegar or alcohol into the medium water of the purifier according to the types of toxins contained in the haze so as to achieve the purpose of washing or neutralizing the toxins, or remove harmful substances in the haze from the air. However, the air purifier is generally placed indoors for use, has a small purification area and cannot be used outdoors.
Disclosure of Invention
The invention provides a nano zero-valent iron bubble which can be used outdoors and has a large purification area, and aims to solve the problems that the air purification area is small and the air purification can not be used for outdoor air purification in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme: the nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 60-80 parts of water, 8-12 parts of nano iron suspension, 4-7 parts of sodium polyacrylate, 3-5 parts of cocamidopropyl amine oxide, 1-2 parts of white vinegar, 1-3 parts of kason, 2-4 parts of glycerol and 3-7 parts of modified methyl cellulose.
The nanometer iron suspension bubble can catch and float in atmospheric harmful haze fine particle matter, utilizes soap bubble to float the principle, and soap bubble can fully with float in the air in the floating dust contact and make it depend on the bubble surface, breaks out when soap bubble and becomes the micro-droplet and is taken away from the air, realizes that the haze particulate matter of large tracts of land in the air is got rid of. Under the static weather condition, adopt unmanned aerial vehicle, helicopter or high altitude platform transmission nanometer iron air bubble can catch haze granule in the air and become to condense the liquid drop, realize that haze fine particle is caught and carry out neutralization and get rid of the toxin immediately in the liquid phase from gaseous phase suspension state and fall back to ground, realize the purification to a large scale of air. Sodium polyacrylate and cocamidopropyl amine oxide are used as surfactants, so that the surface tension of water can be greatly reduced, and bubbles are easily formed; the white vinegar is used for adjusting the pH value of the solution to make the solution acidic and has the functions of disinfection and sterilization; the cason is used as a preservative for the solution; the glycerin can thicken the water film of the bubbles, and the modified methyl cellulose is used as a thickening agent, so that the bubbles are not easy to break. The functions and effects of the nano zero-valent iron are as follows: the nano iron particles can degrade organic pollutants in the air captured by air bubbles, such as hydrocarbon and oxynitride, and can be further decomposed into carbon dioxide and water in the presence of a surfactant and an oxidant; meanwhile, the dust and heavy metal ions in the air can be adsorbed, so that the dust and heavy metal ions are converted into non-polluted particles and fall back to the ground surface. The zero-valent nano iron particle suspension can capture haze and degrade the haze by using air bubbles at one time to neutralize the pollution of heavy metal ions, and the haze is eluted from the air.
Preferably, the preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 70-80 ℃, wherein the mass ratio of the chrysanthemum to water is 10-30 g/L, adding ethanol, the volume ratio of the water to the ethanol is 1: 0.15-0.2, stirring, and soaking to obtain a primary chrysanthemum solution; (2) filtering the primary chrysanthemum solution by using a filter screen to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.2-0.3 mol/L, wherein the volume ratio of chrysanthemum filtering solution to ferric salt aqueous solution is 1: 0.05-1, and oscillating and shaking uniformly to obtain zero-valent nano-iron suspension.
The chrysanthemum contains phenolic chemical substances and has reducibility, high-valence iron ions can be reduced into zero-valent iron, zero-valent iron suspension is formed, the environment is protected, raw materials are saved, the nano zero-valent iron suspension has the characteristics of multifunctional removal of heavy metal ions and degradation of organic matters, organic pollutants in air captured by air bubbles can be degraded in the presence of a surfactant, the organic matters are decomposed into carbon dioxide and water, and meanwhile, dust and heavy metal ions in the air can be adsorbed and converted into non-polluted particles to fall back to the ground surface.
Preferably, the step (1) is carried out for 1-2 h after stirring.
Preferably, the mesh number of the filter screen in the step (2) is 250-300 meshes.
Preferably, the preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 5-12 g of dried methyl cellulose into 120-160 mL of 90-95% ethanol solution by mass fraction, and stirring for 15-20 min to obtain a methyl cellulose solution;
(b) adding 4-8 g of sodium hydroxide into a methyl cellulose solution, raising the temperature to 30-45 ℃, and alkalizing;
(c) adding 0.2-0.6 g of epoxy heptachlor into the methylcellulose alkalized solution, controlling the temperature at 60-70 ℃, stirring for reaction, then adding 0.2-0.3 mol/L of dilute hydrochloric acid for neutralization to neutrality, and performing suction filtration and drying to obtain the modified methylcellulose.
Methyl cellulose is used as a thickening agent and added into a combined liquid, so that bubbles are not easy to break in the air, but the combined liquid has poor thermal stability and acid resistance and is easy to deteriorate; in addition, the methylhemine grafted by the heptanedioxyethane also improves the viscosity of the methylcellulose, enhances the thickening effect of the methylcellulose, ensures that bubble water is not easy to break, prolongs the existence time of the bubble water in the air, and absorbs more haze particle substances.
Preferably, the step (b) is performed for alkalization for 2-3 h.
Preferably, the stirring reaction in the step (c) is carried out for 1-2 h.
Therefore, the invention has the following beneficial effects: (1) the nano-iron suspension bubbles can capture harmful haze fine particulate matters floating in the atmosphere, and by utilizing the soap bubble floating principle, the soap bubbles can be fully contacted with dust floating in the air and attached to the surfaces of the bubbles, and when the soap bubbles are broken and changed into micro-droplets to be taken away from the air, the haze fine particulate matters in the air in a large area are removed; (2) the chrysanthemum contains phenolic chemical substances, has reducibility, can reduce high-valence iron ions into zero-valent iron to form zero-valent iron suspension, is green and environment-friendly, saves raw materials, has the characteristics of multifunctional heavy metal ion removal and organic matter degradation, and can capture haze particles in air and change the haze particles into condensed liquid drops; (3) the methyl cellulose is grafted by the heptanedioxyethane, so that the molecular weight of the methyl cellulose is improved, the heat resistance and the acid resistance of the methyl cellulose are improved, the viscosity of the methyl cellulose is also improved, the thickening effect of the methyl cellulose is enhanced, bubble water is not easy to break, the time of the bubble water in the air is prolonged, and more haze particle substances are absorbed.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 60 parts of water, 8 parts of nano-iron suspension, 4 parts of sodium polyacrylate, 3 parts of cocamidopropyl amine oxide, 1 part of white vinegar, 1 part of kason, 2 parts of glycerol and 3 parts of modified methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 70 ℃, wherein the mass ratio of the chrysanthemum to the water is 10g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.15, stirring and soaking for 1h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 250 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.2mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.05, and oscillating and shaking up to obtain zero-valent nano-iron suspension.
The preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 5g of dried methyl cellulose into 120mL of 90% ethanol solution with mass fraction, and stirring for 15min to obtain a methyl cellulose solution;
(b) adding 4g of sodium hydroxide into a methylcellulose solution, raising the temperature to 30 ℃, and alkalizing for 2 hours;
(c) adding 0.2g of epoxy heptadecane into the methylcellulose alkalized solution, controlling the temperature at 60 ℃, stirring for reaction for 1h, then adding 0.2mol/L of dilute hydrochloric acid for neutralization to neutrality, and obtaining the modified methylcellulose after suction filtration and drying.
Example 2
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 65 parts of water, 9 parts of nano-iron suspension, 5 parts of sodium polyacrylate, 3 parts of cocamidopropyl amine oxide, 1 part of white vinegar, 1 part of kason, 2 parts of glycerol and 4 parts of modified methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 72 ℃, wherein the mass ratio of the chrysanthemum to the water is 15g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.16, stirring and soaking for 1.2h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 260 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.22mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.1, and oscillating and shaking up to obtain the zero-valent nano-iron suspension.
The preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 7g of dried methyl cellulose into 130mL of 92% ethanol solution with mass fraction, and stirring for 16min to obtain a methyl cellulose solution;
(b) adding 5g of sodium hydroxide into a methylcellulose solution, raising the temperature to 35 ℃, and alkalizing for 2.2 h;
(c) adding 0.3g of epoxy heptadecane into the methylcellulose alkalized liquid, controlling the temperature at 62 ℃, stirring for reaction for 1.2h, then adding 0.22mol/L of dilute hydrochloric acid for neutralization to neutrality, and obtaining the modified methylcellulose after suction filtration and drying.
Example 3
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 70 parts of water, 10 parts of nano-iron suspension, 5.5 parts of sodium polyacrylate, 4 parts of cocamidopropyl amine oxide, 1.5 parts of white vinegar, 2 parts of kason, 3 parts of glycerol and 5 parts of modified methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 75 ℃, wherein the mass ratio of the chrysanthemum to the water is 20g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.17, stirring and soaking for 1.5h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 270 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.25mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.5, and oscillating and shaking up to obtain the zero-valent nano-iron suspension.
The preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 8g of dried methyl cellulose into 140mL of 93% ethanol solution by mass fraction, and stirring for 17min to obtain a methyl cellulose solution;
(b) adding 6g of sodium hydroxide into a methylcellulose solution, raising the temperature to 40 ℃, and alkalizing for 2.6 hours;
(c) adding 0.4g of epoxy heptadecane into the methylcellulose alkalized liquid, controlling the temperature at 65 ℃, stirring for reaction for 1.6h, then adding 0.25mol/L of dilute hydrochloric acid for neutralization to neutrality, and obtaining the modified methylcellulose after suction filtration and drying.
Example 4
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 75 parts of water, 11 parts of nano-iron suspension, 6 parts of sodium polyacrylate, 5 parts of cocamidopropyl amine oxide, 2 parts of white vinegar, 3 parts of kason, 4 parts of glycerol and 6 parts of modified methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 78 ℃, wherein the mass ratio of the chrysanthemum to the water is 25g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.18, stirring and soaking for 1.8h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 280 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.28mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.8, and oscillating and shaking up to obtain zero-valent nano-iron suspension.
The preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 10g of dried methyl cellulose into 150mL of 94% ethanol solution with mass fraction, and stirring for 18min to obtain a methyl cellulose solution;
(b) adding 7g of sodium hydroxide into the methylcellulose solution, raising the temperature to 42 ℃, and alkalizing for 2.8 h;
(c) adding 0.5g of epoxy heptadecane into the methylcellulose alkalized liquid, controlling the temperature at 68 ℃, stirring for reaction for 1.8h, then adding 0.28mol/L of dilute hydrochloric acid for neutralization to neutrality, and obtaining the modified methylcellulose after suction filtration and drying.
Example 5
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 80 parts of water, 12 parts of nano-iron suspension, 7 parts of sodium polyacrylate, 5 parts of cocamidopropyl amine oxide, 2 parts of white vinegar, 3 parts of kason, 4 parts of glycerol and 7 parts of modified methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 80 ℃, wherein the mass ratio of the chrysanthemum to the water is 30g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.2, stirring and soaking for 2 hours to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 300 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.3mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:1, and oscillating and shaking up to obtain zero-valent nano-iron suspension.
The preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 12g of dried methyl cellulose into 160mL of ethanol solution with the mass fraction of 95%, and stirring for 20min to obtain a methyl cellulose solution;
(b) adding 8g of sodium hydroxide into a methylcellulose solution, raising the temperature to 45 ℃, and alkalizing for 3 hours;
(c) adding 0.6g of epoxy heptadecane into the methylcellulose alkalized solution, controlling the temperature at 70 ℃, stirring for reaction for 2 hours, then adding 0.3mol/L of dilute hydrochloric acid for neutralization to neutrality, and obtaining the modified methylcellulose after suction filtration and drying.
Comparative example 1
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 70 parts of water, 10 parts of nano-iron suspension, 5.5 parts of sodium polyacrylate, 4 parts of cocamidopropyl amine oxide, 1.5 parts of white vinegar, 2 parts of kason and 3 parts of glycerol.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 75 ℃, wherein the mass ratio of the chrysanthemum to the water is 20g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.17, stirring and soaking for 1.5h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 270 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.25mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.5, and oscillating and shaking up to obtain the zero-valent nano-iron suspension.
Comparative example 2
The nano zero-valent iron bubble is prepared from the following raw materials in parts by weight: 70 parts of water, 10 parts of nano-iron suspension, 5.5 parts of sodium polyacrylate, 4 parts of cocamidopropyl amine oxide, 1.5 parts of white vinegar, 2 parts of kason, 3 parts of glycerol and 5 parts of methyl cellulose.
The preparation method of the nano-iron suspension comprises the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 75 ℃, wherein the mass ratio of the chrysanthemum to the water is 20g/L, then adding ethanol, the volume ratio of the water to the ethanol is 1:0.17, stirring and soaking for 1.5h to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen with the mesh number of 270 meshes to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.25mol/L, wherein the volume ratio of chrysanthemum filtering solution to the ferric salt aqueous solution is 1:0.5, and oscillating and shaking up to obtain the zero-valent nano-iron suspension.
The retention time of bubbles prepared by mixing the components of examples 1-5, comparative example 1 (no modified methyl cellulose added in the component) and comparative example 2 (methyl cellulose is not modified) in the air at normal temperature is as follows:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Time(s) | 123 | 115 | 124 | 118 | 121 | 20 | 65 |
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The nano zero-valent iron bubble is characterized by being prepared from the following raw materials in parts by weight: 60-80 parts of water, 8-12 parts of nano iron suspension, 4-7 parts of sodium polyacrylate, 3-5 parts of cocamidopropyl amine oxide, 1-2 parts of white vinegar, 1-3 parts of kason, 2-4 parts of glycerol and 3-7 parts of modified methyl cellulose; the preparation method of the modified methyl cellulose comprises the following steps:
(a) adding 5-12 g of dried methyl cellulose into 120-160 mL of 90-95% ethanol solution by mass fraction, and stirring for 15-20 min to obtain a methyl cellulose solution;
(b) adding 4-8 g of sodium hydroxide into a methyl cellulose solution, raising the temperature to 30-45 ℃, and alkalizing;
(c) adding 0.2-0.6 g of epoxy heptachlor into the methylcellulose alkalized solution, controlling the temperature at 60-70 ℃, stirring for reaction, then adding 0.2-0.3 mol/L of dilute hydrochloric acid for neutralization to neutrality, and performing suction filtration and drying to obtain the modified methylcellulose.
2. The nano zero-valent iron bubble of claim 1, wherein the nano iron suspension is prepared by a method comprising the following steps:
(1) adding dried chrysanthemum into deionized water, heating to 70-80 ℃, wherein the mass ratio of the chrysanthemum to water is 10-30 g/L, adding ethanol, the volume ratio of the water to the ethanol is 1: 0.15-0.2, stirring, and soaking to obtain a primary chrysanthemum solution;
(2) filtering the primary chrysanthemum solution by using a filter screen to obtain primary filtrate, and then carrying out secondary filtration on the primary filtrate by using vacuum negative pressure to obtain chrysanthemum extracting solution;
(3) adding the chrysanthemum extracting solution into ferric salt aqueous solution with the concentration of 0.2-0.3 mol/L, wherein the volume ratio of chrysanthemum filtering solution to ferric salt aqueous solution is 1: 0.05-1, and oscillating and shaking uniformly to obtain zero-valent nano-iron suspension.
3. The nano zero-valent iron bubble as claimed in claim 2, wherein the nano zero-valent iron bubble is soaked for 1-2 hours after being stirred in the step (1).
4. The nano zero-valent iron bubble of claim 2, wherein the number of the filter meshes in the step (2) is 250-300 meshes.
5. The nano zero-valent iron bubble according to claim 1, wherein the step (b) is performed for alkalization for 2-3 hours.
6. The nano zero-valent iron bubble as claimed in claim 1, wherein the reaction is stirred in step (c) for 1-2 h.
7. Use of nano zero-valent iron bubbles according to any one of claims 1 to 6, wherein the nano zero-valent iron bubbles are used for haze removal in air.
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| CN113820151A (en) * | 2021-08-06 | 2021-12-21 | 南京工业大学 | Method for detecting leakage point of fan filtering unit by using multiple unmanned aerial vehicles |
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