KR102668710B1 - Method for producing ozone-containing luminol salt - Google Patents

Abstract

The present invention relates to a method for producing a luminol salt containing ozone, and is characterized in that luminol, which is insoluble in water, is produced into a luminol salt containing ozone, which is water-soluble and has strong sterilizing power.

Description

Method for producing ozone-containing luminol salt}

The present invention relates to a method for producing luminol salts, and to a method for producing ozone-containing luminol salts that produce ozone with strong sterilizing power.

Ozone (O ₃ ) is a colorless, odorless gas that causes odor and is composed of three oxygen atoms. Originally, ozone is produced naturally, and the concentration of ozone that can be naturally produced is known to be approximately 10 to 20 ppb. It is highly reactive and unstable, so it decomposes immediately not long after it is created.

Ozone was first used for water treatment in the Netherlands in 1893. Since then, ozone has been frequently used as a disinfectant and oxidizing agent in European countries and the United States. However, as chlorine, which is widely used as a tap water disinfectant, reacts with organic matter and generates disinfection by-products, the use of ozone as a disinfectant is increasing as laws and regulations on this are strengthened and regulations on tap water disinfection are strengthened.

Ozone is the second most powerful oxidizing agent after hydroxyl free radical among chemicals used in water treatment and can oxidize many organic and inorganic substances in water. These organic and inorganic substances increase ozone demand. Therefore, in order to maintain residual ozone in water, an amount exceeding the ozone demand by these organic and inorganic substances must be injected.

Ozone is not very soluble in water. Ozone is more soluble in water than oxygen, but compared to chlorine, ozone's solubility is 12 times lower. The solubility of 100% ozone is 570 mg/L at 20℃. The concentration of ozone, which is mainly used in water treatment, is generally less than 14%. Therefore, the mass transfer rate is lower than that of 100% ozone gas, so the ozone concentration in water during water treatment is generally between 0.1 mg/L and 1 mg/L.

In addition, in the method of cultivating plants, water mixed with ozone is evenly sprayed through a sprayer into the plant cultivation containers located on the plant cultivation, thereby sterilizing the plants without using various pesticides or various chemical disinfectants harmful to the human body. In addition to cultivating pollution-free plants, it is also used as a method of growing plants that do not cause environmental pollution.

However, ozone is an unstable molecule and must be generated on-site for use. Ozone is created by combining oxygen atoms (O) and oxygen molecules (O ₂ ). This reaction is endothermic and requires a significant amount of energy. Ozone can be created through several paths, but the most commonly used ozone generation method is using corona discharge. Corona discharge is a form of oxygen-containing gas flowing between two electrodes separated by a discharge gap. When electricity is applied to the electrode, electrons flow between the discharge gaps. The energy of these electrons separates oxygen molecules and forms ozone. In order to produce ozone like this, a lot of energy and equipment are required.

Korean Patent Publication No. 2008-0110349 Japanese Patent No. 4873755

The purpose of the present invention is to provide a method for producing luminol salts that can produce ozone with excellent yield and purity and strong sterilizing power through a simplified production process.

The method for producing ozone-containing luminol salt according to the present invention includes the steps of a) dispersing 2.0 g of 3-Aminophthalhydrazide as luminol in 100 mL of ethanol and adding 1.41 mL of rubidium hydroxide (RbOH) as an alkali metal hydroxide; b) adding water in the reaction amount of 0.59 mL and refluxing for 1 day; c) a stirring step of stirring after refluxing in step b), which includes a first stirring step of stirring for 1 day and a second stirring step of stirring for an additional 1 day at room temperature after the first stirring step; d) a filtering step of filtering the reactant for which secondary stirring has been completed by completing the first stirring step and the second stirring step; and e) recrystallizing the resulting reactant after filtering in step d) in a solution of ethanol and water mixed in a 1:1 (v/v) ratio, thereby producing a rubidium luminol salt represented by Formula 1. It is characterized by obtaining.

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According to the present invention, by improving the chemical reactivity of luminol through optimal reaction conditions, reaction factors, and reaction tank, by-products can be minimized and purity reduction due to partial heating can be prevented, and ozone with excellent purity and yield and strong sterilizing power can be produced. A manufacturing method for producing a luminol salt is provided.

In addition, since the ozone produced in the present invention is water-soluble and contained within the material, it can be used as an ozone production material to sterilize various bacteria in wastewater and purify water supply and seawater.

Figure 1 is a photograph of luminol salt (cyan) observed with the naked eye according to Example 1 of the present invention.
Figure 2 shows data analyzing the structure of the luminol salt obtained in Example 1 by ¹ HNMR. ¹ HNMR (300.133 MHz, D ₂ O): δ 7.25 (t, 2H), 7.043 (d, 1H), 6.67 (d, 1H), 4.642 (s, 1 =5H; 2 =14H; 3 =5H; 4 =6H; 5 =6H).
Figure 3 shows data analyzing the structure of the luminol salt obtained in Example 1 using X-ray crystallography (XRC).
Figure 4 shows data analyzing the structure of the luminol salt obtained in Comparative Example using X-ray crystallography (XRC).
Figure 5 is a flowchart showing the method for producing the luminol salt of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Various embodiments of the present disclosure are described below in conjunction with the accompanying drawings. Various embodiments of the present disclosure can make various changes and have various embodiments, and specific embodiments are illustrated in the drawings and related detailed descriptions are described. However, this is not intended to limit the various embodiments of the present disclosure to specific embodiments, and should be understood to include all changes and/or equivalents or substitutes included in the spirit and technical scope of the various embodiments of the present disclosure. In connection with the description of the drawings, similar reference numbers have been used for similar components.

Expressions such as “includes” or “may include” that may be used in various embodiments of the present disclosure indicate the presence of the disclosed function, operation, or component, and indicate the presence of one or more additional functions, operations, or components. There are no restrictions on components, etc. In addition, in various implementations of the present disclosure, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but It should be understood that it does not exclude in advance the presence or addition of other features, numbers, steps, operations, components, parts, or combinations thereof.

In various embodiments of the present disclosure, expressions such as “or” include any and all combinations of words listed together. For example, “A or B” may include A, B, or both A and B.

Expressions such as “first,” “second,” “first,” or “second” used in various embodiments of the present disclosure may modify various elements of the various embodiments, but do not limit the elements. No. For example, the above expressions do not limit the order and/or importance of the corresponding components. The above expressions can be used to distinguish one component from another. For example, the first user device and the second user device are both user devices and represent different user devices. For example, a first component may be referred to as a second component, and similarly, the second component may be referred to as a first component without departing from the scope of various embodiments of the present disclosure.

When a component is said to be "connected" or "connected" to another component, it means that the component may be directly connected or connected to the other component, but It should be understood that other new components may exist between the above different components. On the other hand, when a component is said to be "directly connected" or "directly connected" to another component, it will be understood that no new components exist between the component and the other component. You should be able to.

Terms used in the various embodiments of the present disclosure are merely used to describe specific embodiments and are not intended to limit the various embodiments of the present disclosure. Singular expressions include plural expressions unless the context clearly dictates otherwise.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the various embodiments of the present disclosure pertain.

Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with the meanings they have in the context of the related technology, and unless clearly defined in various embodiments of the present disclosure, are not ideal or excessively formal. It is not interpreted as meaning.

Hereinafter, the present invention will be described in detail with reference to FIGS. 1 to 5.

The method for producing an ozone-containing luminol salt according to the present invention includes the steps of adding an alkali metal hydroxide to a dispersion in which luminol is dispersed; And it may include adding water and refluxing to obtain luminol alkali metal salt represented by Chemical Formula 1.

Specifically, as shown in FIG. 5, it may include dispersing luminol in ethanol, adding alkali metal hydroxide, adding water to reflux, stirring, filtering, and recrystallizing. You can.

In the step of dispersing luminol in ethanol, luminol, for example, 3-aminophthalhydrazide or 5-amino-2,3-dihydro-1,4-phthalazinedione, is mixed with liquid ethanol, n-propanol, isopropanol, ethyl acetate, and butyl acetate. , ethyl lactate, and butyl lactate.

Luminol, 5-amino-2,3-dihydro-1,4-phthalazinedione, has been used to detect blood stains at existing crime scenes, and has served as a sensor due to its luminescent effect due to oxidation of iron in hemoglobin. In addition to these uses, it is a substance that has numerous other uses, from environmental to medical.

Luminol itself is poorly soluble, and even a small amount of dissolved luminol tends to precipitate after a few days. Additionally, it is sensitive to light, high temperatures, and metal cations. Because of this, there are limitations to its use, but this can be overcome by dispersing it in ethanol and using it, as in the present invention.

Here, it may be most preferable to disperse luminol in ethanol, but it may also be dispersed in one or more selected from n-propanol, isopropanol, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate.

In the step of adding alkali metal hydroxide, luminol is dispersed in ethanol and then alkali metal hydroxide in an aqueous solution is added. The alkali metal hydroxide includes, for example, lithium hydroxide (LiOH), sodium hydroxide (NaOH), and francium hydroxide (FrOH). , cesium hydroxide (CsOH), and rubidium hydroxide (RbOH).

Among these, it may be most preferable to synthesize rubidium luminol salt, an alkali metal salt of luminol, by adding rubidium hydroxide (RbOH) in terms of yield and purity, and in terms of the effect of containing ozone with excellent sterilizing power. As an example, rubidium luminol salt containing ozone with strong sterilizing power can be produced by reacting insoluble luminol with rubidium hydroxide (RbOH) to a water-soluble luminol salt by adding an equivalent amount of water as an additive in the presence of ethanol. .

In the step of adding water and refluxing, after adding the alkali metal hydroxide, water is added, and the equivalent amount of water is added and refluxed for 1 day.

The stirring step includes a first stirring step of stirring for 1 day and a second stirring step of stirring the mixture at room temperature for an additional day.

In the filtering step, the above-mentioned first and second stirring steps are completed and the reactants for which the second stirring has been completed are filtered.

In the recrystallization step, the resulting reactant is recrystallized in a solution of ethanol and water mixed in a 1:1 (v/v) ratio, thereby synthesizing a luminol salt represented by Chemical Formula 1, obtained in the form shown in Figure 1. You can do it.

[Formula 1]

C ₈ H ₁₀ N ₃ O ₄

In the above formula, X is a substituent selected from Li, Na, Fr, Cs, and Rb.

According to the production method of the present invention, the luminol salt represented by Chemical Formula 1 can be synthesized. In particular, as an example, as a result of observing the structure of rubidium luminol salt by X-ray crystallography (XRC), it can be seen in Figure 3 As can be seen, the rubidium luminol salt environment contains ozone without hydrogen atoms inside the pores of the structure, and specifically has a double crystallographic axis passing through the hydrogen atoms of water molecules, with one water molecule as shown in Figure 3. It can be confirmed that oxygen is composed of O8a, O8b, O8c, and O8d at four positions in the ratio of 0.389(3): 0.265(5): 0.179(5): 0.166(5).

For example, in the production of the rubidium luminol salt (in Formula 1, X=Rb), it can be synthesized by the production method shown in Scheme 1.

[Scheme 1]

As such, in the case of the luminol salt according to Chemical Formula 1 prepared by the production method according to the present invention, ozone is generated. This ozone is an element created by combining three oxygen atoms and has strong oxidizing power.

It can be used to remove bacteria or disinfect, and after use, it decomposes into oxygen, making it environmentally friendly. Ozone's strong oxidizing power can also perform complex deodorizing, sterilizing, and bleaching functions, making it useful in daily life and various industries. It can be used in various ways.

The strong oxidizing power of ozone destroys the cell walls of bacteria and other bacteria upon contact and renders them non-renewable. It can also decompose synthetic detergent ingredients such as pesticides and herbicides in a short period of time, so it has the advantage of being applicable to various areas related to sterilization and disinfection. there is. In addition, it is excellent at removing various heavy metals such as iron and arsenic and toxic chemicals such as benzene, and it can easily break the aromatic benzene ring, so it has excellent decolorizing and deodorizing effects, so it can be applied to sewage treatment facilities.

Here, the present invention will be described in more detail through examples. However, the examples are only for illustrating the present invention in detail and are not limited thereto.

[Example 1] Preparation of rubidium luminol salt using rubidium hydroxide (RbOH)

2.0 g of Luminol (3-Aminophthalhydrazide) was dispersed in 100 mL of ethanol in a 250 mL one neck flask. Then, 1.41 mL of RbOH (Alfa Aesar, 50 wt % w/w aq. soln. 99.6 + %) was added, and 0.59 mL of water (the reaction amount) was added and refluxed for 1 day. Next, the mixture was stirred for 1 day and then stirred at room temperature for 1 day. Finally, after filtering the reactant, the resulting reactant was recrystallized in a solution of ethanol and water mixed in a 1:1 (v/v) ratio.

The obtained rubidium luminol salt was confirmed through ¹ H-NMR and X-ray crystallography (XRC), as shown in Table 1 and Figures 1 to 3.

In this way, it was confirmed through the photograph in FIG. 1 that the luminol salt according to Example 1 of the present invention was manufactured in the form of a powder capable of generating ozone. In addition, the structure of the rubidium luminol salt according to Example 1 was analyzed using ¹ HNMR (Varian Mercury Plus 300 spectrometer 300.0 MHz for ¹ H, in D ₂ O) ( ¹ HNMR (300.133 MHz, D ₂ O): δ 7.25 ( t, 2H), 7.043 (d, 1H), 6.67 (d, 1H), 4.642 (s, 1 =5H; 2 =14H; 3 =5H; 4 =6H; 5 =6H)) can be seen in Figure 2 In addition, as a result of observing the structure of the rubidium luminol salt using , Specifically, it has a double crystallographic axis that passes through the hydrogen atom of the water molecule, and one water molecule has oxygen at four positions as O8a, O8b, O8c, and O8d, as shown in Figure 3, 0.389(3): 0.265( It was confirmed that the ratio was 5): 0.179(5): 0.166(5).

[Example 2] Preparation of cesium luminol salt using cesium hydroxide (CsOH)

Luminol (5-Amino-2,3-dihydro-1,4-phthalazined) was added to a 250 mL one neck flask.

ione) 1.0 g was dispersed in 100 mL of ethanol. Then, 1.00 mL of CsOH (Sigma aldrich, 50 wt % w/w aq. soln. 99.9 + %) was added, and 0.45 mL of water (the reaction amount) was added and refluxed for 1 day. Next, the mixture was stirred for 1 day and then stirred at room temperature for 1 day. Finally, after filtering the reactant, the resulting reactant was recrystallized in a solution of ethanol and water mixed in a 1:1 (v/v) ratio to complete the preparation of cesium luminol salt according to Formula 1.

[Comparative Example] Preparation of potassium luminol salt using potassium hydroxide (KOH)

2.0 g of Luminol (3-Aminophthalhydrazide) was dispersed in 100 mL of ethanol in a 250 mL one neck flask. Then, 1.41 mL of 30% (w/v) KOH potassium hydroxide (Aldrich, 85+%) was added, and 0.59 mL of water (the reaction amount) was added and refluxed for 1 day. Next, the mixture was stirred for 1 day and then stirred at room temperature for 1 day. Finally, after filtering the reactant, the resulting reactant was recrystallized in a solution of ethanol and water mixed in a 1:1 (v/v) ratio. And it was confirmed through Figure 4 and Table 2 that the obtained potassium luminol salt did not contain ozone.

[Experimental Example 1] Test of sterilizing effect of luminol salt

Using the luminol salt prepared in Examples and Comparative Examples as a sample, in order to test its bactericidal effect against Staphylococcus aureus, one colony was collected from the Baird-Parker agar medium of the selected test bacteria and added to 5 ml of culture medium. After inoculation, it was cultured at 35-37°C for 18-24 hours. This culture solution itself was diluted 10,000 times with TSB, and 2 ml was dispensed into each sterile test tube. Next, 0, 25, 50, 100, and 500 μl of the luminol salts prepared in Examples 1 and 2 and Comparative Examples were added in liquid form, respectively, and cultured at 35 to 37°C for 18 to 24 hours. The reacted culture solution was diluted 10,000 times with physiological saline, and 20 ㎕ was spread on plate count agar and cultured at 35-37°C for 18-24 hours, and then the sterilizing effect was measured by counting the grown colonies. . Accordingly, the results of counting the number of colonies of the sterilizing effect of luminol salt on Staphylococcus aureus can be confirmed through Tables 3 to 5.

division Example 1
0㎕ Example 1
25㎕ Example 1
50㎕ Example 1
100㎕ Example 1
500㎕ 0 days 852 107 0 0 0 15th 518 0 0 0 0

division Example 2
0㎕ Example 2
25㎕ Example 2
50㎕ Example 2
100㎕ Example 2
500㎕ 0 days 852 506 312 178 0 15th 518 398 194 53 0

division Comparative example
0㎕ Comparative example
25㎕ Comparative example
50㎕ Comparative example
100㎕ Comparative example
500㎕ 0 days 852 852 852 852 852 15th 518 521 519 517 520

Unit: Colony form unit (CFU) As can be seen in Tables 3 to 5 above, in the case of rubidium luminol salt containing ozone according to the present invention (Example 1), bacteria were immediately formed even at 50 ㎕ on the day of manufacture (day 0). No bacteria were detected at all, and in the case of Example 1, even after 15 days, no bacteria were detected in all sections (25-500㎕), and it was found that the excellent sterilizing power was maintained.

In addition, in the case of the cesium luminol salt according to Example 2, no bacteria were detected at all even in 500 ㎕ on the day of manufacture (day 0), and in the case of Example 2, no bacteria were detected at all in 500 ㎕ even after 15 days. It was confirmed that this was not the case.

However, in the case of the comparative example, it was confirmed that the synthesized potassium luminol salt did not contain ozone and therefore did not provide this sterilizing effect at all.

[Experimental Example 2] Test of sterilizing effect of luminol salt

The luminol salt prepared in Examples and Comparative Examples was used as a sample to test its sterilizing effect on Escherichia coli in the same manner as in Experimental Example 1. The results of counting the number of colonies are shown in Tables 6 to 8. You can check it.

division Example 1
0㎕ Example 1
25㎕ Example 1
50㎕ Example 1
100㎕ Example 1
500㎕ 15th 734 347 125 0 0

division Example 2
0㎕ Example 2
25㎕ Example 2
50㎕ Example 2
100㎕ Example 2
500㎕ 15th 734 526 402 298 0

division Comparative example
0㎕ Comparative example
25㎕ Comparative example
50㎕ Comparative example
100㎕ Comparative example
500㎕ 15th 734 731 733 734 737

Unit: Colony form unit (CFU)

As can be seen in Tables 6 to 8 above, in the case of the rubidium luminol salt containing ozone according to the present invention (Example 1), no bacteria were detected in 100 ㎕ even after 15 days, and in Example 2 In the case of the cesium luminol salt, it was confirmed that no bacteria were detected in 500 ㎕ even after 15 days.

However, in the case of the comparative example, it was confirmed that the synthesized potassium luminol salt did not contain ozone, so it did not provide this sterilizing effect at all.

As such, according to the present invention, as can be seen through FIGS. 1 to 3, a production method capable of synthesizing a luminol salt containing ozone is provided. In addition, through the production method of FIG. 5, it is possible to produce a luminol salt containing ozone with excellent purity and yield and strong sterilizing power.

Claims (6)

a) dispersing 2.0 g of 3-Aminophthalhydrazide as luminol in 100 mL of ethanol and adding 1.41 mL of rubidium hydroxide (RbOH) as an alkali metal hydroxide;
b) adding water in the reaction amount of 0.59 mL and refluxing for 1 day;
c) a stirring step of stirring after refluxing in step b), which includes a first stirring step of stirring for 1 day and a second stirring step of stirring for an additional 1 day at room temperature after the first stirring step;
d) a filtering step of filtering the reactant for which secondary stirring has been completed by completing the first stirring step and the second stirring step; and
e) After filtering in step d), the resulting reactant is recrystallized in a solution of ethanol and water mixed in a 1:1 (v/v) ratio to obtain rubidium luminol salt represented by Formula 1. A method for producing an ozone-containing luminol salt, characterized in that:
[Formula 1]
C ₈ H ₁₀ N ₃ O ₄ Rb delete delete delete delete delete