High-efficiency ozone-removing liquid catalyst, preparation method and application thereof

Abstract

The application belongs to the technical field of catalysts, and relates to a high-efficiency ozone-removing liquid catalyst as well as a preparation method and application thereof.The preparation method comprises the following steps: 1) adding a flavonoid compound into an ethanol solution, heating and stirring to obtain a mixed solution; 2) adding an organic salt compound into the mixed solution, uniformly stirring, evaporating the solvent, and performing suction filtration and drying on the product to obtain a powder; and 3) dissolving the powder by using a solvent, then adding a stabilizer, and obtaining a target product.The liquid catalyst is prepared by using the flavonoid compound and the organic salt compound, ozone is formed at an outlet to form a liquid seal, high-concentration ozone is efficiently decomposed and removed, the preparation process condition is simple, and the cost is low.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalysts, and relates to a high-efficiency ozone-removing liquid catalyst as well as a preparation method and application thereof. BACKGROUND

[0002] Ozone is a trace gas in the atmosphere, which is mainly located in the stratosphere of the atmosphere, and an ozone layer also exists. Ozone plays an important role in the ecological system of the earth and human health. It can absorb ultraviolet radiation from the sun, which greatly reduces the probability of human skin cancer, cataract and other diseases on the earth's surface. However, if the ozone concentration in the human living environment is too high, it will have the opposite effect. High-concentration ozone can stimulate the respiratory tract, cause irritation and pain in the eyes and nasal cavity; long-term exposure to high-concentration ozone can also cause inflammation and oxidative damage to lung tissue, especially for the elderly and children, greatly reducing their immunity, damaging vascular endothelial cells and increasing the risk of cardiovascular disease.

[0003] At present, with the increasing development of science and technology and the continuous improvement of industrialization, a large amount of ozone is generated in a large number of industrial production areas, which causes a large amount of irreversible harm to human health. In particular, a large amount of ozone is formed by photochemical reaction of vehicle exhaust and some organic compounds, and ozone is generated by various reactions in industrial production areas. Therefore, it is urgent to control and manage the ozone generated in these places, and to decompose high-concentration ozone into harmless substances, so that the ozone concentration is reduced to within the range required by the environment.

[0004] In order to reduce the threat of high-concentration ozone to people, some common methods are currently used, such as adsorption method, thermal decomposition method, plasma decomposition method and radiation decomposition method.

[0005] (1) The adsorption method includes two ways. One is to use the porous structure and high surface area of the porous material to have adsorption performance. The preparation of such porous material is complex and has high cost. In addition, it is greatly affected by external temperature, pressure and other factors. When ozone is chemically adsorbed on the porous material, the active sites for absorbing ozone are easily damaged. Therefore, this method generally has large energy consumption, which is the reason why this kind of material cannot be widely applied. The other way is to absorb ozone by chemical solution, such as liquid potassium iodide, phenoxazine and sodium thiosulfate, which can absorb ozone through a series of chemical reactions. However, the waste liquid after reaction of this method is usually not environmentally friendly, and the treatment cost is high.

[0006] (2) The thermal decomposition method is to react with ozone by heating to produce harmless oxygen, and the radiation decomposition method is to react with ozone by ultraviolet radiation to produce harmless oxygen. However, the conditions required by these two methods are harsh, and they cannot efficiently and quickly control high-concentration ozone.

[0007] (3) Plasma decomposition method is to first adsorb ozone, then concentrate, and finally convert it into nitrogen and argon, generate non-thermal plasma, so as to degrade ozone; but this method uses plasma equipment which is relatively expensive, and the operation is relatively complex, and the generated nitrogen oxide will still pollute the air.

[0008] In summary, although the existing ozone elimination method can achieve the purpose of eliminating ozone, it has the following problems: (1) low elimination efficiency, difficult to achieve the purpose of removing high concentration ozone in the environment; (2) the preparation of the existing ozone decomposition material or catalyst is harsh, the process is complex, and the cost is high; (3) harmful to the environment, poor safety. SUMMARY

[0009] In order to solve the technical problems of low efficiency and high processing cost of existing ozone elimination, the present application provides a kind of high-efficiency ozone-removing liquid catalyst and its preparation method and application.

[0010] The present application uses flavonoids and organic salt compounds to prepare a liquid catalyst, which can form a liquid seal at the ozone outlet to achieve efficient decomposition and removal of high-concentration ozone. The preparation process is simple and low in cost.

[0011] In order to achieve the above purpose, the technical scheme adopted by the present application is:

[0012] A preparation method of a high-efficiency ozone-removing liquid catalyst, comprising the following steps:

[0013] 1) Add flavonoids to ethanol solution, heat and stir to obtain a mixed solution; the mass fraction of flavonoids in each mL of ethanol solution is 2% to 6%;

[0014] 2) Add organic salt compound to the mixed solution and stir evenly, then evaporate the solvent, and then extract and dry the obtained product to obtain a powder; the mass ratio of the organic salt compound to the flavonoids is 0.1 to 0.32;

[0015] 3) Dissolve the powder with a solvent, then add a stabilizer to obtain the target product; the volume of the solvent is 10 ml to 200 ml per gram of powder, and the mass of the stabilizer is 1% to 10% of the total mass of the flavonoids and the organic salt compound.

[0016] In step 1), the flavonoids are one or more of quercetin, ginkgetin, myricetin, isofraxidin and rotenone.

[0017] In step 1), the heating temperature is 30°C to 60°C, and the stirring time is 20 min to 50 min.

[0018] The organic salt compound in the step 2) is one or more of sodium cholate, potassium gluconate, sodium gluconate and potassium dihydrogen citrate.

[0019] In the step 2), the stirring time is 10 min to 30 min; the solvent evaporation temperature is 55 DEG C to 70 DEG C; the suction filtration time is 10 min to 20 min, the drying temperature is 40 DEG C to 60 DEG C, and the drying time is 3 h to 6 h.

[0020] In the step 3), the stabilizer is ethylenediaminetetraacetic acid and / or phosphate buffer.

[0021] In the step 3), the solvent is a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4.

[0022] The high-efficiency ozone-removing liquid catalyst is prepared by the preparation method of the high-efficiency ozone-removing liquid catalyst.

[0023] The high-efficiency ozone-removing liquid catalyst is applied to decompose ozone.

[0024] Further limited, at room temperature, the high-efficiency ozone-removing liquid catalyst decomposes ozone in a closed environment for 25 min to 32 min, and the ozone concentration decreases from 1200 mg / h to below 10 ppm.

[0025] The high-efficiency ozone-removing liquid catalyst and the preparation method can be applied to environmental ozone treatment.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] 1. The liquid catalyst is prepared by using flavonoid compounds and organic salt compounds, and the synergistic effect of the organic metal salt and the flavonoid compounds enhances the decomposition of ozone.

[0028] 2. The liquid catalyst is prepared by using mixing, evaporation, filtration and drying, and the reaction conditions are mild.

[0029] 3. The liquid ozone-removing catalyst prepared by the present application still has high decomposition effect on high-concentration ozone after being stored for more than 10 months.

[0030] 4、The liquid catalyst of the present application can realize the decomposition and elimination of ozone at normal temperature by spraying, and the area of contact with ozone is increased by spraying, thereby enhancing the efficiency of eliminating ozone; and the liquid catalyst does not need to be heated, and is more convenient to use.

[0031] 5、The raw materials used in the preparation of the present application are mainly flavonoid compounds and organic salt compounds, which are easy to obtain and non-toxic, and the prepared liquid catalyst does not produce harmful factors to the environment, and is safe. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a graph of the change of ozone concentration with time in a closed environment using a certain commercial ozone decomposer;

[0033] Figure 2 is a graph of the change of ozone concentration with time in a closed environment in Example 3;

[0034] Figure 3 is the results of the catalyst stability test. DETAILED DESCRIPTION

[0035] The present application provides a preparation method of the high-efficiency ozone-removing liquid catalyst, which comprises the following steps.

[0036] 1) Flavonoid compounds are added to an ethanol solution, and heated and stirred to obtain a mixed solution; the mass fraction of the flavonoid compounds in each mL of the ethanol solution is 2% to 6%.

[0037] In this step, the flavonoid compounds are one or more of quercetin, ginkgetin, myricetin, glycyrrhizin and rotenone.

[0038] It can be understood that: the flavonoid compounds can be any one of the above five kinds; or any two of them, for example: quercetin and ginkgetin, quercetin and myricetin, quercetin and glycyrrhizin, quercetin and rotenone, myricetin and glycyrrhizin, ginkgetin and myricetin, ginkgetin and glycyrrhizin, ginkgetin and rotenone, myricetin and glycyrrhizin, etc.; or any three of them, for example: quercetin, ginkgetin and myricetin, quercetin, ginkgetin and glycyrrhizin, ginkgetin, myricetin and glycyrrhizin, ginkgetin, myricetin and rotenone, etc.; or any four of them, for example: quercetin, ginkgetin, myricetin and glycyrrhizin, ginkgetin, myricetin, glycyrrhizin and rotenone, quercetin, myricetin, glycyrrhizin and rotenone, quercetin, ginkgetin, myricetin and rotenone, etc.; or all of the five.

[0039] When the flavonoid compounds are multiple combinations, the multiple substances are combined in any ratio.

[0040] In this step, when the flavonoids are added into the ethanol solution, the mass fraction of the flavonoids in each mL of the ethanol solution is 2%, 3%, 4%, 5%, or 6%.

[0041] In this step, the volume concentration of the ethanol solution is 75%.

[0042] In this step, the heating temperature is 30-60°C, and the stirring time is 20-50 min. In practice, the heating temperature can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C; and the stirring time can be 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min.

[0043] 2) The organic salt compound is added into the mixed solution and stirred uniformly, and then the solvent is evaporated, and the obtained product is subjected to suction filtration and drying to obtain a powder.

[0044] In this step, the mass ratio of the organic salt compound to the flavonoids is 0.1-0.32.

[0045] In this step, the organic salt compound is a soluble organic compound composed of an organic anion and a metal cation. Specifically, the organic salt compound is one or more of sodium cholate, potassium gluconate, sodium gluconate, and potassium dihydrogen citrate.

[0046] It can be understood that the organic salt compound is any one of the above four kinds; it can also be a combination of any two, for example: sodium cholate and potassium gluconate, sodium cholate and sodium gluconate, sodium cholate and potassium dihydrogen citrate, potassium gluconate and sodium gluconate, potassium gluconate and potassium dihydrogen citrate, and sodium gluconate and potassium dihydrogen citrate; it can also be a combination of any three, for example: sodium cholate, potassium gluconate, and sodium gluconate, sodium cholate, potassium gluconate, and potassium dihydrogen citrate, potassium gluconate, sodium gluconate, and potassium dihydrogen citrate; or a combination of the four.

[0047] When the organic salt compound is in multiple combinations, the multiple substances are combined in any ratio.

[0048] In this step, the stirring time is 10-30 min; the solvent evaporation temperature is 55-70°C; the suction filtration time is 10-20 min, the drying temperature is 40-60°C, and the drying time is 3-6 h.

[0049] 3) The powder is dissolved in a solvent, and then a stabilizer is added to obtain the target product.

[0050] In this step, the volume of solvent is 10ml-200ml / g powder, and the mass of the stabilizer is 1%-10% of the total mass of flavonoids and organic salt compounds.

[0051] In this step, the stabilizer is ethylenediaminetetraacetic acid and / or phosphate buffer.

[0052] In this step, the solvent is a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4.

[0053] The high-efficiency ozone-removing liquid catalyst prepared by the application has good decomposition effect on ozone in a closed environment at room temperature, and can be applied to ozone treatment of the environment. Its application range is extremely wide and is not limited by the form of the support, and the reaction space can be fully utilized, for example, by spraying or liquid sealing method; preferably, in the form of spraying to increase the contact area with ozone so as to make the ozone elimination efficiency higher, and to efficiently point-to-point decompose high-concentration ozone from the source.

[0054] The following describes the liquid catalyst provided by the application and the high-efficiency decomposition and elimination performance of high-concentration ozone in several groups of preferred embodiments, but this cannot be regarded as a limitation on the protection scope of the application.

[0055] In the following examples, the conventional operations in the field are used to realize, for example, stirring, mixing, heating, etc. if not otherwise specified.

[0056] In the following examples, the medicines and reagents used are all analytical pure products purchased in the market.

[0057] Example 1

[0058] In this embodiment, the preparation method of the high-efficiency ozone-removing liquid catalyst comprises the following steps.

[0059] 1) 4.53g quercetin is added to 44.3ml ethanol solution (the volume concentration of the ethanol solution is 75%) to prepare a solution, which is placed in a 40℃ water bath and stirred at 200r / min for 30min to obtain a mixed solution.

[0060] 2) After the mixed solution is cooled to room temperature, 1.21g of sodium cholate is added and stirred for 10min, and then the solution is evaporated at 60℃, after which it is repeated three times, and then the obtained material is vacuum filtered for 10min, and then placed in a 40℃ oven for drying for 3h to obtain a powder.

[0061] 3) The powder is dissolved in 10ml of self-prepared solution (a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4) and dispersed, and then 0.51g of sodium laurate is added and stirred for 10min to obtain the monoketone liquid catalyst.

[0062] The liquid catalyst prepared in the embodiment is used to decompose ozone.

[0063] The specific decomposition process is: 2ml of the liquid catalyst (concentration of 0.12g / ml-0.14g / ml) is diluted 20 times, and is sprayed in a 10cm*10cm*2cm closed environment with 1200mg / h ozone, and the ozone concentration in the closed environment is less than 10ppm for 26min40s.

[0064] Embodiment 2

[0065] In the embodiment, the preparation method of the liquid catalyst for efficiently removing ozone includes the following steps.

[0066] 1) 3.54g of ginkgetin, 2.47g of myricetin are added into 42.7ml of ethanol solution to prepare a solution, which is placed in a 45℃ water bath and stirred at 300r / min for 35min to obtain a mixed solution.

[0067] 2) After the mixed solution is cooled to room temperature, 1.34g of sodium cholate is added and stirred for 15min, and then the solution is evaporated at 60℃, and then the operation is repeated twice, and then the obtained substance is vacuum filtered for 15min, and then is placed in a 50℃ oven and dried for 5h to obtain a powder.

[0068] 3) The powder is dissolved in 16.2ml of a self-prepared solution (a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4) and dispersed, and finally 0.34g of ethylenediaminetetraacetic acid is added and stirred for 20min to obtain the liquid catalyst of diketone.

[0069] The liquid catalyst prepared in the embodiment is used to decompose ozone.

[0070] The specific decomposition process is: 2ml of the liquid catalyst (concentration of 0.12g / ml-0.14g / ml) is diluted 20 times, and is sprayed in a 10cm*10cm*2cm closed environment with 1200mg / h ozone, and the ozone concentration in the closed environment is less than 10ppm for 26min40s.

[0071] Embodiment 3

[0072] In the embodiment, the preparation method of the liquid catalyst for efficiently removing ozone includes the following steps.

[0073] 1) 1.52g of quercetin, 1.95g of ginkgetin, 2.55g of glycyrrhizin are added into 44.3ml of ethanol solution (volume concentration of the ethanol solution is 75%) to prepare a solution, which is placed in a 40℃ water bath and stirred at 150r / min for 25min to obtain a mixed solution.

[0074] 2) After the mixed solution is cooled to room temperature, 0.23 g of potassium gluconate and 0.46 g of sodium cholate are added and stirred for 10 min, then the solution is evaporated at 60°C, after which the process is repeated twice, then the obtained substance is vacuum filtered for 16 min, and then placed in a 55°C oven for drying for 6 h to obtain a powder.

[0075] 3) The obtained powder is dissolved in 11.7 ml of a self-prepared solution (a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4) and dispersed, then 0.42 g of ethylenediaminetetraacetic acid is added and stirred for 25 min to obtain the liquid trione catalyst.

[0076] The liquid catalyst prepared in this embodiment is used for decomposing ozone.

[0077] The specific decomposition process is: 2 ml of the liquid trione catalyst (concentration of 0.12 g / ml-0.14 g / ml) is diluted 20 times and sprayed in a 10 cm x 10 cm x 2 cm closed environment generating 1200 mg / h of ozone, and the ozone concentration in the closed environment is less than 10 ppm for 32 min.

[0078] Example 4

[0079] In this embodiment, the preparation method of the high-efficiency ozone-removing liquid catalyst comprises the following steps.

[0080] 1) 1.03 g of quercetin, 1.97 g of ginkgetin, 2.54 g of myricetin, and 0.58 g of glycyrrhizin are added to 42.8 ml of an ethanol solution (volume concentration of the ethanol solution is 75%) to prepare a solution, which is placed in a 55°C water bath and stirred at 100 r / min for 20 min to obtain a mixed solution.

[0081] 2) After the mixed solution is cooled to room temperature, 0.50 g of sodium gluconate and 0.72 g of potassium gluconate are added, and after the solute is completely dissolved, the solution is evaporated by heating to 60°C, then the process is repeated three times, then the obtained substance is vacuum filtered for 20 min, and then placed in a 60°C oven for drying for 4 h to obtain a powder.

[0082] 3) The obtained powder is dissolved in 12.5 ml of a self-prepared solution (a mixture of anhydrous ethanol and pure water in a volume ratio of 1:4) and dispersed, then 0.21 g of sodium laurate and 0.18 g of ethylenediaminetetraacetic acid are added and stirred at room temperature for 20 min to obtain the liquid tetrone catalyst.

[0083] The liquid catalyst prepared in this embodiment is used for decomposing ozone.

[0084] The specific decomposition process is: taking 2ml of the five-ketone liquid catalyst (concentration of 0.12g / ml-0.14g / ml) diluted by 20 times, spraying in a 10cm*10cm*2cm closed environment with 1200mg / h ozone, and continuously spraying for 29min20s to make the ozone concentration in the closed environment lower than 10ppm.

[0085] Example 5

[0086] In this embodiment, the preparation method of the high-efficiency ozone-removing liquid catalyst comprises the following steps.

[0087] 1) 1.24g of quercetin, 0.47g of ginkgetin, 2.14g of myricetin, 1.86g of isomyricetin, and 1.33g of rotenone were added into 42.3ml of an ethanol solution (volume concentration of the ethanol solution was 75%) to prepare a solution, which was placed in a 50℃ water bath and stirred at 200r / min for 25min to obtain a mixed solution.

[0088] 2) After the mixed solution was cooled to room temperature, 0.22g of potassium dihydrogen citrate and 0.45g of sodium gluconate were added and stirred for 20min, then the solution was evaporated at 60℃, and then the obtained substance was repeatedly evaporated three times, and then vacuum filtration was performed for 20min, and then the obtained substance was placed in a 60℃ oven and dried for 5.5h to obtain a powder.

[0089] 3) The obtained powder was dissolved in 13.4ml of a self-prepared solution (anhydrous ethanol and pure water were mixed according to a volume ratio of 1:4) and dispersed, and finally 0.12g of sodium laurate and 0.33g of ethylenediaminetetraacetic acid were added and stirred for 15min to obtain a five-ketone liquid catalyst.

[0090] The liquid catalyst prepared in this embodiment was used for ozone decomposition.

[0091] The specific decomposition process is: taking 2ml of the five-ketone liquid catalyst (concentration of 0.12g / ml-0.14g / ml) diluted by 20 times, spraying in a 10cm*10cm*2cm closed environment with 1200mg / h ozone, and continuously spraying for 29min20s to make the ozone concentration in the closed environment lower than 10ppm.

[0092] The performance of the liquid catalyst prepared in the application was further verified.

[0093] Verification 1

[0094] The ozone decomposition performance test of the liquid catalyst prepared in Example 3 and a certain commercial ozone decomposer was carried out in a fixed reactor.

[0095] Sample: The three-ketone high-efficiency ozone-removing liquid catalyst prepared in Example 3 was diluted by 20 times.

[0096] And a certain commercial ozone decomposing agent as a comparison; XRF analysis, the main components of a certain commercial ozone decomposing agent are: w (Na) 97.60%, w (Al) 0.299%, w (Si) 0.447%, w (S) 0.180%, w (Ca) 0.328%, w (Zn) 1.15%.

[0097] The specific process is: the liquid catalyst diluted 20 is placed in 10cm*10cm*2cm environment, then the outlet end of the ozone machine generating 1200mg / h is completely immersed in the liquid, then the ozone decomposition efficiency is observed by timing and the standard curve is drawn in the later stage; under the same conditions, a certain commercial ozone decomposing agent is operated in the same way to draw a curve; as shown in Figure 1 and Figure 2 , Figure 1 is the ozone decomposition efficiency curve of a certain commercial ozone decomposing agent, Figure 2 is the ozone decomposition efficiency curve of the liquid catalyst prepared in example 3.

[0098] From the results of Figure 1 and Figure 2 , for the same mass fraction of ozone removal solvent, the liquid ozone removal efficiency of the present application is higher and more stable, indicating that the ozone removal agent prepared by the present application has more extensive application value.

[0099] Verification 2

[0100] The liquid catalyst prepared in example 3 is selected and placed for more than 10 months, then the oxygen decomposition efficiency curve is tested according to the conditions in verification 1, as shown in Figure 3 .

[0101] Referring to Figure 3 , the liquid catalyst is placed for more than 10 months, and the ozone decomposition efficiency is still high. It is proved that the liquid catalyst prepared by the present application has good stability.

[0102] The above is only a preferred embodiment of the present application, not any limitation on the present application, any simple modification, change and equivalent change according to the technical essence of the present application to the above embodiment are still within the protection scope of the technical solution of the present application.

Claims

1. A process for the preparation of a high efficiency ozone-depleting liquid catalyst, characterized by, The method comprises the following steps: 1) adding flavonoids into an ethanol solution, heating and stirring to obtain a mixed solution; the mass fraction of flavonoids in the ethanol solution is 2%-6% per mL; 2) adding an organic salt compound into the mixed solution and stirring uniformly, then evaporating the solvent, and performing suction filtration and drying on the obtained product to obtain a powder; the mass ratio of the organic salt compound to the flavonoids is 0.1-0.32; 3) dissolving the powder with a solvent, then adding a stabilizer to obtain a target product; the volume of the solvent is 10-200 mL / g of the powder, and the mass of the stabilizer is 1%-10% of the total mass of the flavonoids and the organic salt compound; in the step 1), the flavonoids are one or more of quercetin, ginkgetin, myricetin, glycyrrhizin and rotenone; in the step 2), the organic salt compound is one or more of sodium cholate, potassium gluconate, sodium gluconate and dihydrogen potassium citrate.

2. The method of claim 1, wherein the high-efficiency ozone-depleting liquid catalyst is prepared by the steps of: in the step 1), the heating temperature is 30-60 DEG C, and the stirring time is 20-50 min.

3. The method of claim 1, wherein the high-efficiency ozone-depleting liquid catalyst is prepared by the steps of: in the step 2), the stirring time is 10-30 min, the solvent evaporation temperature is 55-70 DEG C, the suction filtration time is 10-20 min, the drying temperature is 40-60 DEG C, and the drying time is 3-6 h.

4. The method of claim 1, wherein the high-efficiency ozone-depleting liquid catalyst is prepared by the steps of: in the step 3), the stabilizer is ethylenediaminetetraacetic acid and / or a phosphate buffer.

5. The method for preparing the high-efficiency deodorizing liquid catalyst according to claim 1, characterized in that, in the step 3), the solvent is a mixture of anhydrous ethanol and pure water in a volume ratio of 1:

4.

6. The high-efficiency ozone-removing liquid catalyst prepared by the preparation method of the high-efficiency ozone-removing liquid catalyst according to claim 1.

7. The application of the high-efficiency ozone-removing liquid catalyst according to claim 6 in decomposing ozone.

8. Use according to claim 7, characterized in that, At normal temperature, the high-efficiency ozone-removing liquid catalyst can decompose ozone in a closed environment for 25-32 min, and the ozone concentration is reduced from 1200 mg / h to below 10 ppm.

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