阅读说明：本技术 一种过渡金属固体酸空气杀菌剂及其制备方法与应用 (Transition metal solid acid air bactericide and preparation method and application thereof ) 是由 安胜欣 周泽安 李文志 于 2020-12-31 设计创作，主要内容包括：本发明涉及环境净化技术领域,尤其涉及一种过渡金属固体酸空气杀菌剂及其制备方法。本发明提供了一种过渡金属固体酸空气杀菌剂的制备方法：将金属氧化物混合后煅烧得前驱体,置于硝酸溶液中进行震荡,反应后离心,去除上清液得到固体层状前驱体,并用水冲洗固体层状前驱体至中性；然后将其置于水中搅拌,加入四丁基氢氧化铵溶液后进行震荡,离心得上清液,在上清液中滴加硝酸溶液至上清液中至沉淀不再增加,离心收集沉淀,真空干燥后,得固体酸,将固体酸与前驱物溶液混合即得过渡金属固体酸空气杀菌剂。本发明生产工艺简单温和、且可回收,且二氧化氯的释放时间长。(The invention relates to the technical field of environmental purification, in particular to a transition metal solid acid air bactericide and a preparation method thereof. The invention provides a preparation method of a transition metal solid acid air bactericide, which comprises the following steps: mixing and calcining metal oxides to obtain a precursor, placing the precursor in a nitric acid solution for oscillation, centrifuging after reaction, removing supernatant to obtain a solid layered precursor, and washing the solid layered precursor with water to be neutral; and then placing the mixture into water, stirring, adding tetrabutylammonium hydroxide solution, then oscillating, centrifuging to obtain supernatant, dropwise adding nitric acid solution into the supernatant until precipitation is not increased any more, centrifuging to collect precipitate, vacuum drying to obtain solid acid, and mixing the solid acid with precursor solution to obtain the transition metal solid acid air bactericide. The invention has simple and mild production process, can be recycled and has long release time of the chlorine dioxide.)

1. The transition metal solid acid air bactericide is characterized by comprising the following raw materials in parts by weight: 1-5 parts of solid acid and 1-25 parts of precursor solution;

the solid acid comprises the following raw materials: li₂CO₃The addition ratio of the elements A and B is 1-30: 5-15 in turn.

2. The transition metal solid acid air sanitizer according to claim 1, wherein said element is selected from the group consisting ofElement A being Ta₂O₅Or Nb₂O₅。

3. The transition metal solid acid air sanitizer according to claim 1, wherein said element B is MoO₃Or WO₃。

4. The transition metal solid acid air sanitizer according to claim 1, wherein the precursor solution is a chlorite solution with a mass concentration of 5-20% or a chlorate solution with a mass concentration of 5-20%.

5. The method for preparing a transition metal solid acid air sanitizer according to any one of claims 1 to 4, comprising the steps of:

(1) proportionally mixing the weighed Li₂CO₃Mixing the element A and the element B, and calcining to obtain a precursor;

(2) placing the precursor obtained in the step (1) in a nitric acid solution for oscillation, reacting for 10-18 days, centrifuging, removing supernatant to obtain a solid layered precursor, and washing the solid layered precursor with water to be neutral;

(3) putting the solid layered precursor obtained in the step (2) into water, stirring uniformly, then adding a tetrabutylammonium hydroxide solution, oscillating, centrifugally collecting a supernatant after the reaction is finished, dropwise adding a nitric acid solution into the supernatant until the precipitate is not increased any more, centrifugally collecting the precipitate, and drying in vacuum at the temperature of 40-60 ℃ for 10-14 hours to obtain a solid acid;

(4) and (4) mixing the solid acid obtained in the step (3) with the precursor solution according to a proportion to obtain the transition metal solid acid air bactericide.

6. The preparation method according to claim 5, wherein the calcination temperature in the step (1) is 550-800 ℃; the calcination time is 12-72h, and the temperature rise rate during calcination is 3 ℃/min.

7. The method according to claim 5, wherein the concentration of the nitric acid in the step (2) or the step (3) is 0.5 to 1.5 mol/L.

8. The method according to claim 5, wherein in the step (3), the shaking time is 10 to 18 days; tetrabutylammonium hydroxide solution is added to adjust the pH to 9.5-10.

9. The preparation method according to claim 5, wherein in the step (2), the mass-to-volume ratio of the precursor to the nitric acid is 1: 5-15g/mL, and the same volume of nitric acid solution is replaced every 4 days during the reaction.

10. The use of a transition metal solid acid air disinfectant as claimed in any one of claims 1 to 9, wherein the transition metal solid acid air disinfectant is used by using nitrogen as carrier gas at a flow rate of 300-700mL/min, and adding deionized water at appropriate time during the release period.

Technical Field

The invention relates to the technical field of environmental purification, in particular to a transition metal solid acid air bactericide, and a preparation method and application thereof.

Background

The safe and long-acting realization of environmental purification becomes the focus of worldwide attention. The traditional disinfectant has the defects of high toxicity, heavy smell and the like, and serious people have the risk of cancer. Chlorine dioxide (ClO) as a strong oxidant₂) The high-efficiency, spectral and safe chemical disinfectants identified by the world health organization are widely applied. However, the physical properties of chlorine dioxide are peculiar, and chlorine dioxide is often used in the form of an aqueous solution thereof for disinfection and sterilization. The form generally needs to be prepared at present, has short release period, is inconvenient in the processes of storage, transportation and use, and cannot fully exert the inherent advantages of strong efficacy, wide diffusion range and the like of the gaseous chlorine dioxide. Therefore, the development of the chlorine dioxide solid preparation has very important significance.

The conventional chlorine dioxide solid preparation is mainly prepared by mixing chlorite and an acidifying agent together to react to generate chlorine dioxide, the system can react at room temperature and can generate chlorine dioxide with higher concentration in a short time, wherein the acidifying agent is an indispensable component and mainly comprises solid acid and liquid acid, and the liquid acid is difficult to popularize and use due to the problems of equipment corrosion, safe use, difficult recovery, inconvenient transportation and the like. Commonly used solid acidifying agents are, for example, citric acid, oxalic acid, tartaric acid, AlCl₃For example, such solid acids are generally used by dissolving in water to react with chlorite in the form of an aqueous solution, and although they are easier to transport than liquid acids, they still have the problem of being difficult to recycle. In addition, in order to stably release chlorine dioxide and improve the problems of short release period and the like, solid adsorbents such as silica gel, molecular sieve, high water absorption polyacrylamide resin, sodium carboxymethylcellulose and the like are often added into a reaction system, so that the whole preparation process of chlorine dioxide is complicated and the cost is increased.

Patent application No. 201910156295.4 provides a chlorine dioxide preservative gel and a preparation method thereof, wherein A, B two gel layers are prepared, and A, B two gels are attached to release chlorine dioxide when in use. Wherein the solid acids contained in the B-layer sol include tartaric acid, citric acid and oxalic acid. The preparation process of the B-layer gel is that solid acid is firstly dissolved in acid water and finally mixed with glutaraldehyde water solution to prepare the B-layer gel. Compared with the invention, the solid acid is water-soluble solid acid, although existing in a solid form and easy to transport, existing in a water-soluble form in the using process, similar to inorganic acid, and the acid can not be recovered after the reaction is finished, thus not meeting the requirements of environmental protection.

The patent application No. 201910420422.7 discloses a preparation method and application of a chlorine dioxide disinfectant containing supported solid acid, wherein concentrated hydrochloric acid, a template agent, 0.5-2.5 parts of attapulgite, tetraethoxysilane and water level raw materials are stirred for 20-24h at 35-40 ℃, reacted for 24h at 100 ℃, filtered, washed, calcined for 5-7h at 550 ℃ with 500-; then mixing with solid acid, stirring at 30-35 ℃ for 4-12h, drying at 60-120 ℃ for 4-5h, and calcining at 300-400 ℃ for 3-4h to finally obtain the supported solid acid. Firstly, the preparation process relates to strong acid, and the problems of equipment corrosion, safety and the like exist; secondly, the preparation steps of the load type solid acid are multiple, and the process is complex.

Therefore, how to provide a long-release, safe and green air disinfectant is a problem that needs to be solved by those skilled in the art.

Disclosure of Invention

The invention aims to provide a transition metal solid acid air bactericide which is simple in preparation process, safe, green and long in release time, and a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention firstly provides a transition metal solid acid air bactericide which comprises the following raw materials in parts by weight: 1-5 parts of solid acid and 1-25 parts of precursor solution;

the solid acid comprises the following raw materials: li₂CO₃The addition ratio of the elements A and B is 1-30: 5-15 in turn.

Preferably, the transition metal solid acid air bactericide comprises the following raw materials in parts by weight: 1-5 parts of solid acid and 1-15 parts of precursor solution.

Preferably, the element A is Ta₂O₅Or Nb₂O₅。

Preferably, the element B is MoO₃Or WO₃。

Preferably, the precursor solution is a chlorite solution with the mass concentration of 5-20% or a chlorate solution with the mass concentration of 5-20%.

Further preferably, the precursor solution is a chlorite solution with a mass concentration of 5-15% or a chlorate solution with a mass concentration of 5-15%.

Further preferably, the precursor solution is a chlorite solution with a mass concentration of 7-10% or a chlorate solution with a mass concentration of 7-10%.

More preferably, the chlorate is one of potassium chlorate, sodium chlorate and magnesium chlorate.

The invention further provides a preparation method of the transition metal solid acid air bactericide, which comprises the following steps:

(1) proportionally mixing the weighed Li₂CO₃Mixing the element A and the element B, and calcining to obtain a precursor; the temperature rise rate during calcination is 3 ℃/min;

(2) placing the precursor obtained in the step (1) in a nitric acid solution for oscillation, reacting for 10-18 days, centrifuging, removing supernatant to obtain a solid layered precursor, and washing the solid layered precursor with water to be neutral;

(3) putting the solid layered precursor obtained in the step (2) into water, stirring uniformly, then adding a tetrabutylammonium hydroxide solution, oscillating, centrifugally collecting a supernatant after the reaction is finished, dropwise adding a nitric acid solution into the supernatant until the precipitate is not increased any more, centrifugally collecting the precipitate, and drying in vacuum at the temperature of 40-60 ℃ for 10-14 hours to obtain a solid acid;

(4) and (4) mixing the solid acid obtained in the step (3) with the precursor solution according to a proportion to obtain the transition metal solid acid air bactericide.

Preferably, the calcination temperature in the step (1) is 550-800 ℃; the calcination time is 12-72 h.

Further preferably, the calcination temperature is 580-700 ℃.

Further preferably, the calcination temperature is 580 to 650 ℃.

Further preferably, the calcination time is 12-48 h.

Further preferably, the calcination time is 12-36 h.

Preferably, in the step (2) or the step (3), the concentration of the nitric acid is 0.5-1.5 mol/L.

Preferably, in the step (3), the shaking time is 10 to 18 days.

Preferably, in the step (3), tetrabutylammonium hydroxide solution is added to adjust the pH to 9.5-10.

Preferably, in the step (2), the mass-to-volume ratio of the precursor to the nitric acid is 1: 5-15g/mL, and the nitric acid solution with the same volume is replaced every 4 days during the reaction.

Preferably, in the step (2) or (3), the shaking reaction is performed at room temperature.

More preferably, in the step (1), the weighed Li is proportioned at room temperature₂CO₃Mixing the element A and the element B, putting the mixture into a ceramic pot, and putting the ceramic pot into a muffle furnace for calcining.

Further, the invention also provides application of the transition metal solid acid air bactericide, wherein when the transition metal solid acid air bactericide is used, nitrogen is used as carrier gas, the flow rate is 300-700mL/min, and deionized water is supplemented in the releasing period at proper time.

Compared with the prior art, the invention has the following beneficial effects:

1. the preparation method of the solid acid adopted by the invention has simple and mild production process and can be recycled. The solid acid is added into the aqueous solution of sodium chlorite, and the release time of chlorine dioxide can reach 15 days without adding any auxiliary material.

2. Compared with the prior art, the solid acid provided by the invention is insoluble in water, the preparation method is simple, the solid acid is used in a solid chlorine dioxide preparation, only water needs to be added in the middle under the condition of not adding any sustained release agent, and the release time of chlorine dioxide is long and can reach 15 days. And after the reaction is finished, the solid powder can be recovered, and the method is environment-friendly.

3. The patent discloses a preparation method of a transition metal solid acid air bactericide. The transition metal solid acid is prepared by a mild method and is used for preparing the gas chlorine dioxide, the release time can reach more than 15 days under the condition of not reinforcing a solid adsorbent, meanwhile, the solid acid can be recycled, and the existing solid acid for preparing the gas chlorine dioxide is mostly dissolved in water and cannot be recycled after being used.

Drawings

FIG. 1 is a scanning electron microscope scanning image of a solid layered precursor prepared in step (2) of example 1 of the present invention;

FIG. 2 is a scanning electron microscope scan of a solid acid obtained in step (3) of example 1 according to the present invention;

FIG. 3 is a graph showing the bactericidal effect before and after the release of the transition metal solid acid air bactericide prepared in example 1 of the present invention.

Detailed Description

The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

A transition metal solid acid air bactericide comprises the following raw materials in parts by weight: 3 parts of solid acid, 13 parts of precursor solution: a chlorite solution with a mass concentration of 12.5%;

the solid acid comprises the following raw materials: li₂CO₃And an element A: ta₂O₅And element B: MoO₃The adding proportion of the raw materials is 15: 10 in sequence.

A preparation method of a transition metal solid acid air bactericide comprises the following steps:

(1) proportionally mixing the weighed Li₂CO₃Mixing the element A and the element B, and calcining to obtain a precursor; the calcining temperature is 600 ℃; the calcination time is 24 h; the temperature rise rate during calcination is 3 ℃/min;

(2) placing the precursor obtained in the step (1) in a nitric acid solution with the concentration of 1.0mol/L for oscillation (the mass-volume ratio of the precursor to the nitric acid is 1: 10g/mL, and the nitric acid solution with the same volume is replaced every 4 days during the reaction), after reacting for 14 days, centrifuging, removing the supernatant to obtain a solid lamellar precursor, and washing the solid lamellar precursor with water to be neutral;

(3) putting the solid layered precursor obtained in the step (2) into water, stirring uniformly, then adding a tetrabutylammonium hydroxide solution, adjusting the pH to 9.8, oscillating, centrifugally collecting supernatant after reaction is finished, dropwise adding a nitric acid solution with the concentration of 1.0mol/L into the supernatant until precipitation is not increased any more, centrifugally collecting precipitate, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain solid acid;

(4) and (4) mixing the solid acid obtained in the step (3) with the precursor solution according to a proportion to obtain the transition metal solid acid air bactericide.

When the transition metal solid acid air bactericide is used, nitrogen is required to be used as carrier gas, the flow rate is 500mL/min, and deionized water is added in due time during the release period.

Example 2

A transition metal solid acid air bactericide comprises the following raw materials in parts by weight: 1 part of solid acid, 1 part of precursor solution: a chlorate solution having a mass concentration of 5%;

the solid acid comprises the following raw materials: li₂CO₃And an element A: nb₂O₅And element B: WO₃The adding proportion of the raw materials is 1: 5 in turn.

A preparation method of a transition metal solid acid air bactericide comprises the following steps:

(1) proportionally mixing the weighed Li₂CO₃Mixing the element A and the element B, and calcining to obtain a precursor; the calcination temperature is 550 ℃; the calcination time is 12 h; the temperature rise rate during calcination is 3 ℃/min;

(2) placing the precursor obtained in the step (1) in a nitric acid solution with the concentration of 0.5mol/L for oscillation (the mass-volume ratio of the precursor to the nitric acid is 1: 5g/mL, and the nitric acid solution with the same volume is replaced every 4 days during the reaction), after reacting for 10 days, centrifuging, removing the supernatant to obtain a solid lamellar precursor, and washing the solid lamellar precursor with water to be neutral;

(3) putting the solid layered precursor obtained in the step (2) into water, stirring uniformly, then adding a tetrabutylammonium hydroxide solution, adjusting the pH to 9.5, oscillating, centrifugally collecting supernatant after reaction is finished, dropwise adding a nitric acid solution with the concentration of 0.5mol/L into the supernatant until precipitation is not increased any more, centrifugally collecting precipitate, and carrying out vacuum drying at 40 ℃ for 10 hours to obtain solid acid;

(4) and (4) mixing the solid acid obtained in the step (3) with the precursor solution according to a proportion to obtain the transition metal solid acid air bactericide.

When the transition metal solid acid air bactericide is used, nitrogen is required to be used as carrier gas, the flow rate is 300mL/min, and deionized water is added in due time during the release period.

Example 3

A transition metal solid acid air bactericide comprises the following raw materials in parts by weight: 5 parts of solid acid, 25 parts of precursor solution: a 20% chlorite solution;

the solid acid comprises the following raw materials: li₂CO₃And an element A: ta₂O₅Or Nb₂O₅And element B: MoO₃Or WO₃The adding proportion of the raw materials is 30: 15 in sequence.

A preparation method of a transition metal solid acid air bactericide comprises the following steps:

(1) proportionally mixing the weighed Li₂CO₃Mixing the element A and the element B, and calcining to obtain a precursor; the calcining temperature is 800 ℃; the calcination time is 72 h; the temperature rise rate during calcination is 3 ℃/min;

(2) placing the precursor obtained in the step (1) in a nitric acid solution with the concentration of 1.5mol/L for shaking (the mass-volume ratio of the precursor to the nitric acid is 1: 15g/mL, and the nitric acid solution with the same volume is replaced every 4 days during the reaction), after reacting for 18 days, centrifuging, removing the supernatant to obtain a solid lamellar precursor, and washing the solid lamellar precursor with water to be neutral;

(3) putting the solid layered precursor obtained in the step (2) into water, stirring uniformly, then adding a tetrabutylammonium hydroxide solution, adjusting the pH to 10, oscillating, centrifugally collecting supernatant after reaction is finished, dropwise adding a nitric acid solution with the concentration of 1.5mol/L into the supernatant until precipitation is not increased any more, centrifugally collecting precipitate, and carrying out vacuum drying at 60 ℃ for 14 hours to obtain solid acid;

(4) and (4) mixing the solid acid obtained in the step (3) with the precursor solution according to a proportion to obtain the transition metal solid acid air bactericide.

When the transition metal solid acid air bactericide is used, nitrogen is required to be used as carrier gas, the flow rate is 700mL/min, and deionized water is added in due time during the release period.

Example 4

The release time of the transition metal solid acid air bactericide chlorine dioxide obtained by the method is measured by a single-factor experiment.

A transition metal solid acid air disinfectant obtained according to the method of example 1;

the release time of 10 groups of chlorine dioxide was measured by following the procedure of example 1 except that the calcination temperature in step (2) of example 1 was changed to 500 ℃, 550 ℃, 580 ℃, 630 ℃, 650 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃ respectively, and the other conditions were not changed. The results are shown in Table 1.

TABLE 1

Therefore, when the calcination temperature is 600 ℃, the release time of chlorine dioxide is longest and can reach 15 days.

Example 5

The release time of the transition metal solid acid air bactericide chlorine dioxide obtained by the method is measured by a single-factor experiment.

A transition metal solid acid air disinfectant obtained according to the method of example 1;

the method of example 1 was followed except that the calcination time in step (2) of example 1 was changed to 6h, 8h, 12h, 16h, 36h, 48h, 60h, 72h, 80h and 90h, respectively, and the other conditions were not changed, and the release time of chlorine dioxide was measured for 11 groups. The results are shown in Table 2.

TABLE 2

Therefore, when the calcination time is selected to be 24 hours, the release time of the chlorine dioxide is the longest and can reach 15 days.

Example 6

The release time of the transition metal solid acid air bactericide chlorine dioxide obtained by the method is measured by a single-factor experiment.

A transition metal solid acid air disinfectant obtained by the method of example 1 as group 1;

the method of example 1 is followed, but the adding proportions of the solid acid and the precursor solution in the step (1) of example 1 are respectively changed as follows:

2 parts of solid acid and 1 part of precursor solution;

3 parts of solid acid and 3 parts of precursor solution;

3 parts of solid acid and 6 parts of precursor solution;

3 parts of solid acid and 11 parts of precursor solution;

3 parts of solid acid and 15 parts of precursor solution;

3 parts of solid acid and 25 parts of precursor solution;

1 part of solid acid and 25 parts of precursor solution;

1 part of solid acid and 28 parts of precursor solution;

1 part of solid acid and 30 parts of precursor solution;

the other conditions were not changed, and the release time of chlorine dioxide was measured for 10 groups as groups 2 to 10, respectively. The results are shown in Table 3.

TABLE 3

It can be seen that the composition was selected to be 3 parts solid acid, 13 parts precursor solution: when the mass concentration of the chlorite solution is 12.5%, the release time of chlorine dioxide is longest and can reach 15 days.

Example 7

Experiment for verifying bactericidal effect of air bactericide prepared in example 1

Two groups of commercially available air disinfectants were used as comparative example 1.

The air bactericide obtained in example 1 was divided into two groups;

the first group is that the same amount of bacteria is sprayed in a plurality of rooms with the same size, meanwhile, the bacteria amount and the bacteria species in each room are manually controlled to keep a relatively stable state, 10 minutes passes after the bacteria amount and the bacteria species are sprayed, and then the sterilization rate of each room is detected;

the second group is that the same amount of bacteria is sprayed in a plurality of rooms with the same size, meanwhile, the bacteria amount and the bacteria species in each room are manually controlled to keep a relatively stable state, after the bacteria amount and the bacteria species are sprayed, the bacteria species are sprayed for three hours, and then the sterilization rate of each room is detected; the data collection described above is collated to table 4 below.

TABLE 4

	First group sterilization Rate (%)	Second group sterilization Rate (%)
			Example 1	99.5％	93.5％
Comparative example 1	99.2％	87.1％

It can be seen that the sterilization rate of example 1 in the first group is slightly higher than that of comparative example 1, while the sterilization rate of the second group is significantly higher than that of comparative example 1.

The results of the detection of the first group of indoor air escherichia coli in example 1 show that the colony count of the escherichia coli is 0, the sterilization rate of the escherichia coli is 100%,

the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.