WO2012026710A2

WO2012026710A2 - Environmental and nontoxic cleaning solution for storage tank

Info

Publication number: WO2012026710A2
Application number: PCT/KR2011/006101
Authority: WO
Inventors: 김태우
Original assignee: 주식회사그린바이오
Priority date: 2010-08-23
Filing date: 2011-08-18
Publication date: 2012-03-01
Also published as: WO2012026710A3; WO2012026710A9

Abstract

A cleaning solution for a storage tank of the present invention comprises: 100 parts by weight of an organic acid; and 1-10 parts by weight of dodecyl glycerol polyethoxylate represented by chemical formula 1.

Description

Eco-friendly and non-toxic reservoir cleaning liquid

The present invention relates to a reservoir cleaning liquid, and more particularly, to a reservoir cleaning liquid used for periodically cleaning an indoor or outdoor reservoir storing water.

Reservoir is a generic term for a device that stores tap, rain, or river water for use as drinking or living water. Water is stored in the reservoir for a certain period of time, and as the storage period is extended, the inner wall of the reservoir may be contaminated and should be periodically cleaned. The causes of contamination of the reservoirs are varied, such as contamination by precipitation of inorganic salts such as carbonates dissolved in water, contamination by the growth of microorganisms, or contamination by algae such as moss. Physical washing using a brush or a loofah may be used for washing the reservoir, but chemical washing using a cleaning solution containing a specific component is generally used. Chemical cleaning is less labor than physical cleaning, excellent cleaning effect, especially when the cleaning is difficult due to the small entrance.

The cleaning agent mainly composed of an anionic surfactant contains anionic surfactants such as alkanesulfonates, alkyl ether sulphates, and straight chain alkylbenzene sulfonates as the main components, and is composed of fatty acid alkanolamide components as nonionic surfactants and bubble stabilizers. Various additives, such as zeolite and a silicate, are contained. However, such a cleaning liquid containing an anionic surfactant as a main component has a problem in that the acidity of the cleaning liquid itself must be basic and the bubbles are so severe that it is very difficult to use in a water tank, and the basic cleaning liquid cannot remove the deposited inorganic salts.

Another type of cleaner that can solve the problem of basic cleaners is an acidic cleaner. The acidic detergent is an acidic cleaner having an acidity of about 2 to 6, and has an advantage of effectively removing inorganic salts and moss accumulated in the reservoir. Acidic detergents include a variety of acids such as phosphoric acid and alkylenesulfonic acid. Phosphoric acid is not suitable for use as a component of detergents because its use is very limited due to eutrophication of rivers.

Korean Unexamined Patent Publication No. 2007-0104181, which is a domestic prior art document relating to an acidic cleaner, discloses a cleaner for removing organic pollutants from stone or metal materials. A polyoxyethylene oxide condensed nonionic surfactant, a whitening material and a microorganism are disclosed. It contains highly toxic substances such as hydrogen peroxide and hydrofluoric acid or hydrochloric acid for cleaning pollutants. Korean Laid-Open Patent No. 2007-0003854 is a cleaning liquid used after a chemical mechanical polishing (CMP) process, and includes ammonium citrate, ammonium oxalate, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Disclosed is a cleaning liquid containing variously. Korean Laid-Open Patent Publication No. 2005-0053725 discloses that a polyacrylate, a polymer material, can be added to an acidic cleaning solution to remove a contamination of a tile in a bathroom, a toilet, a toilet, or an indoor tile. Korean Laid-Open Patent Publication No. 2001-0015752 discloses a technique for an acidic detergent composition using an alkoxylated amine, wherein the acidic detergent is an alkoxylated aliphatic amine and sulfamic acid, hydrogen peroxide or peracetic acid and nonionic interface to exhibit antimicrobial activity. The activator includes an ethoxylated aliphatic alcohol.

US Patent Publication No. 2008-0045439, an overseas prior art document relating to acidic detergents, includes a citric acid, fatty acid alcohol or polyethoxylate type surfactant, sodium bisulfite, glycerin, etc. Disclosed compositions are disclosed. US Patent Publication No. 2008-0132439 discloses a composition containing diethylene glycol, triethylene glycol, sodium dodecylbenzenesulfonate as an alkyl glycoside, glyceryl, ether, and an organic solvent component. In addition, US Patent Publication No. 2008-0139443 discloses an acidic detergent containing quaternary ammonium salt, citric acid which is an organic acid, glycol methyl ether, ethanol, glycol monobutyl ether, etc. as an organic solvent, wherein the quaternary ammonium salt exhibits antimicrobial activity. It is known.

Among the prior arts for the acidic cleaners, acidic detergents that use strong inorganic acids such as hydrochloric acid and phosphoric acid to give acidity to the cleaners are highly susceptible to environmental pollution, and hydrogen peroxide, peracetic acid, etc. Since it is toxic to the human body, additional efforts are required to remove the cleaning liquid after cleaning. Therefore, there is no need for environmental pollution, and there is a growing need for development of an eco-friendly water tank cleaning agent composed of components having low toxicity to humans.

Accordingly, the problem to be solved by the present invention is to provide a water tank cleaning liquid having excellent cleaning effect without containing toxic substances such as inorganic acids and hydrogen peroxide.

The present invention provides a storage tank cleaning liquid containing 100 parts by weight of an organic acid and 1 to 10 parts by weight of dodecylglycerol polyethoxylate represented by the following formula (1).

Formula 1

(R is an alkyl group having 12 carbon atoms, m, n is an integer, m + n = 2 to 10)

According to an embodiment of the present invention, the organic acid may include 100 parts by weight of citric acid, 5 to 15 parts by weight of ascorbic acid, 70 to 180 parts by weight of glycolic acid and 70 to 180 parts by weight of gluconic acid.

According to another embodiment of the present invention, the organic acid may further include 10 to 30 parts by weight of oxalic acid relative to 100 parts by weight of citric acid.

According to another embodiment of the present invention, the reservoir cleaning liquid may further include dodecylglycerol.

Since the reservoir cleaning liquid of the present invention contains organic acids such as citric acid, ascorbic acid and glycolic acid as a main component, it is very less toxic and less susceptible to environmental pollution compared with the cleaner using inorganic acids. In addition, the dodecylglycerol ethoxylate synthesized by ethoxylating dodecylglycerol without using toxic hydrogen peroxide was used as a nonionic surfactant to secure excellent washing ability.

1 is a ¹ H-NMR measurement results of dodecylglycerol ethoxylate-5 synthesized in accordance with an embodiment of the present invention.

2 is a ¹ H-NMR measurement results of dodecylglycerol ethoxylate-7 synthesized in accordance with an embodiment of the present invention.

3 is a ¹ H-NMR measurement results of dodecylglycerol ethoxylate-10 synthesized in accordance with an embodiment of the present invention.

Figure 4 is a photograph showing the result of the adhesion moss removal experiment using the water tank cleaner of the present invention.

5 is a photograph showing the results of the algae solution experiment using the reservoir cleaning agent of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The reservoir cleaning liquid of the present invention is characterized by comprising 100 parts by weight of an organic acid and 1 to 10 parts by weight of dodecylglycerol polyethoxylate represented by the following formula (1).

Formula 1

The reservoir cleaning liquid of the present invention includes water, an organic acid, and dodecylglycerol polyethoxylate. Water is a solvent of the washing liquid, an organic acid is a component for imparting acidity to the washing liquid, and dodecylglycerol polyethoxylate is a nonionic surfactant. The organic acid includes citric acid, ascorbic acid, glycolic acid and gluconic acid, and the composition ratio is 100 parts by weight of citric acid and 5 to 15 weight of ascorbic acid. It is preferable that they are 70-180 weight part and glycolic acid 70-180 weight part. The mixing ratio of the organic acids can be freely adjusted in the numerical range described, since the main pollutants may vary depending on the use environment of the reservoir can be used by selecting the appropriate mixing ratio. In addition, the organic acid may further include an oxalic acid, and the oxalic acid is preferably included in a component ratio of 10 to 30 parts by weight with respect to 100 parts by weight of citric acid. Since oxalic acid has a function of effectively removing rust and ink contaminants, when oxalic acid is included in the reservoir cleaning liquid, oxalic acid may also have an effect of removing rust that may occur in the metal reservoir. In addition, even a small amount of oxalic acid can increase the cleaning capacity, has the advantage of low cost.

In the present invention, the dodecylglycerol polyethoxylate represented by the formula (1) was synthesized, and by using this, it was possible to develop an acidic detergent having excellent cleaning effect through blending with an organic acid. Dodecylglycerol polyethoxylate was synthesized by the following reaction scheme 1 (scheme 1). Referring to the following Synthesis Scheme 1, dodecylglycerol was synthesized by adding water to the epoxide under basic conditions and ring opening reaction, and ether chain was extended by adding ethylene oxide under basic conditions. Synthesized dodecylglycerol polyethoxylates.

Synthetic Scheme 1

In this case, dodecylglycerol polyethoxylates having different molecular weights may be synthesized according to the equivalent weight of ethylene oxide. For example, when 5 equivalents of ethylene oxide is added to 1 mole of dodecylglycerol, dodecylglycerol polyethoxylate-5 (DGO-5) is synthesized, and when 7 equivalents of ethylene oxide is added, dodecylglycerol polyethoxyl Rate-7 (DGO-7) is synthesized, and dodecylglycerol polyethoxylate-10 (DGO-10) can be synthesized when 10 equivalents of ethylene oxide is added. However, the compound produced when synthesizing the dodecylglycerol polyethoxylate by the above synthesis scheme 1 is not only one kind. For example, when 5 equivalents of ethylene oxide is added to 1 mole of dodecylglycerol, the main product is dodecylglycerol polyethoxylate-5 (DGO-5), but other products having different molecular weights May be present in proportion. In addition, some unreacted dodecylglycerol may be present in the product, which imparts antimicrobial activity to the reservoir cleaning liquid. The antimicrobial effect of dodecylglycerol has been known from the literature (H.S. Ved, et al, The J. Biological Chemistry, 259 (13), 8115-8121, (1984)). Therefore, when the product obtained through the synthesis scheme 1 is added to the water tank washing liquid as it is, the antimicrobial effect can be exerted on the washing liquid to maximize the washing effect. The washing ability is changed depending on the composition ratio of the dodecylglycerol polyethoxylate included in the detergent, and the preferred composition ratio is 100 parts by weight of organic acid and 1 to 10 parts by weight of dodecylglycerol polyethoxylate. If the content ratio of dodecylglycerol polyethoxylate is less than 1 part by weight, the dispersing effect of hydrophobic contaminants by the surfactant is less, and the cleaning ability is lowered. Lowers.

The reservoir cleaning liquid of the present invention may further include LX-94. LX-94 is a product name of a nonionic surfactant manufactured and sold by Hannong-Sung Co., Ltd., and is produced by copolymerizing ethylene oxide and propylene oxide. Since LX-94 is a low-foaming surfactant, it functions to suppress the generation of bubbles in the water tank cleaning operation. Therefore, the addition of an appropriate amount of LX-94 has the effect of suppressing the generation of bubbles in the reservoir cleaning liquid to increase the amount of dodecylglycerol polyethoxylate added. The amount of LX-94 added is preferably about 15 parts by weight or more based on 100 parts by weight of citric acid. This is because when the amount of LX-94 added is too small, the effect of inhibiting bubbles is small and dodecylglycerol polyethoxylate cannot be sufficiently added.

Hereinafter, the present invention will be described in more detail using examples. The embodiments are only intended to describe the present invention in more detail, and the scope of the rights is not limited by the embodiments, and the scope of the rights should be interpreted only by the matters described in the claims.

Example 1-1 (Synthesis of Dodecylglycerol Ethoxylate-5)

1 mole of dodecylglycerol (mw: 260) and 0.1 mole of potassium hydroxide (KOH) were added to a 1 liter high-pressure reactor, and 5 moles of ethylene oxide were maintained for about 6 hours while maintaining the reactor temperature in the range of 120 to 140 ° C. Reacted. Subsequently, after lowering the reaction temperature and the pressure to normal and normal pressure, potassium hydroxide (KOH) was neutralized with about 0.1 mole of acetic acid.

Example 1-2 (Synthesis of Dodecylglycerol Ethoxylate-7)

Synthesis was carried out in the same manner as in Example 1-1, except that the amount of ethylene oxide was changed to 7 mol.

Example 1-3 (Synthesis of Dodecylglycerol Ethoxylate-10)

Synthesis was carried out in the same manner as in Example 1-1, except that the amount of ethylene oxide was changed to 10 mol.

Example 2-1 (Preparation of Cleaning Liquid 1)

Washing liquid 1 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 5 g of GDO-10 in 360 g of water.

Example 2-2 (Preparation of Cleaning Liquid 2)

Washing liquid 2 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 15 g of GDO-10 in 360 g of water.

Example 2-3 (Preparation of Cleaning Liquid 3)

Washing liquid 3 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 25 g of GDO-10 in 360 g of water.

Example 2-4 (Preparation of Cleaning Liquid 4)

Washing liquid 4 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 5 g of GDO-7 in 360 g of water.

Example 2-5 (Preparation of Cleaning Liquid 5)

Washing solution 5 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-95, and 15 g of GDO-7 in 360 g of water.

Example 2-6 (Preparation of Cleaning Liquid 6)

Washing solution 6 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 25 g of GDO-7 in 360 g of water.

Comparative Example (Preparation of Cleaning Liquid 9)

Washing solution 9 was prepared by dissolving 100 g of citric acid, 10 g of ascorbic acid, 100 g of glycolic acid, 20 g of oxalic acid, 100 g of gluconic acid, 15 g of LX-94, and 1 g of GDO-10 in 360 g of water.

In Table 1 below, the components of the Examples and Comparative Examples are collectively shown.

Table 1

Assay Example 1 (of dodecylglycerol ethoxylate-5 ^1One H NMR)

In order to confirm that dodecylglycerol ethoxylate-5 was synthesized according to Example 1-1, ¹ H NMR analysis was performed in a CDCl ₃ solution. 1 is a ¹ H-NMR measurement results of dodecylglycerol ethoxylate-5 synthesized in accordance with an embodiment of the present invention. Referring to Fig. 1, a characteristic peak of dodecylglycerol ethoxylate-5 is observed. From this it can be seen that the main product synthesized according to Example 1-1 is dodecylglycerol ethoxylate-5.

Assay Example 2 (of dodecylglycerol ethoxylate-7 ^1One H NMR)

In order to confirm that dodecylglycerol ethoxylate-7 was synthesized according to Example 1-2, ¹ H NMR analysis was performed in a CDCl ₃ solution. Referring to FIG. 2, the properties of dodecylglycerol ethoxylate-7 Peaks are observed. From this it can be seen that the main product synthesized according to Example 1-2 is dodecylglycerol ethoxylate-7.

Assay Example 3 (of dodecylglycerol ethoxylate-10 ^1One H NMR)

In order to confirm that dodecylglycerol ethoxylate-10 was synthesized according to Example 1-3, ¹ H NMR analysis was performed in a CDCl ₃ solution. Referring to FIG. 3, the properties of dodecylglycerol ethoxylate-10 Peaks are observed. From this it can be seen that the main product synthesized according to Example 1-3 is dodecylglycerol ethoxylate-10.

Experimental Example 1 (residual carbon amount measurement experiment)

Residual carbon content measurement experiments were performed to compare the cleaning ability of the cleaning agents 1 to 6 and the cleaning agents 9 prepared according to Examples and Comparative Examples. After mixing animal oil with vegetable oil and hydrocarbon oil, apply a certain amount on stainless steel plate (2cmX5cm), and then immerse in 600ml (25 ℃) of 5% cleaning solution for 10 minutes, wash once in distilled water, and leave residual carbon on stainless steel plate. (Surface Carbon Determinator RC-212, LECO Corporation) was measured.

The measurement results are summarized in Table 2 below. Referring to Table 2, the cleaning agents prepared in Examples 2-1 to 2-6 (cleaning solution 1 to cleaning solution 6) had a smaller residual carbon amount than the cleaning agents (cleaning solution 9) prepared in Comparative Example. From these results, it can be seen that the washing ability is significantly increased when dodecylglycerol ethoxylate is added to the organic acid.

When dodecylglycerol was compared with the cleaning capacity of the cleaning solution 1, the cleaning solution 4, the cleaning solution 2 and the cleaning solution 5, the cleaning solution 3 and the cleaning solution 6, in which the same amounts of dodecylglycerol ethoxylate-10 and dodecylglycerol ethoxylate-7 were added. The cleaning ability when ethoxylate-10 was added was determined to be slightly higher.

Although not shown in Table 2, when only water was used instead of the cleaning solution, the residual carbon amount of 180.3 was measured.

TABLE 2

Experimental Example 2 (attached moss removal experiment)

Attached moss removal experiment was performed using the cleaning agents prepared in Examples and Comparative Examples. The algae used in the experiments were freshwater microalgae, Scenedesmus sp. The culture was used incubated for about 1.5 months using Allen medium.

For removing the algae attached to the culture vessel wall, the plastic vessel wall was cut out to a predetermined size and then immersed in 50 ml of a 1% washing solution for 9 hours and washed with running tap water. The degree of washing of each piece was as shown in FIG.

Referring to FIG. 4, when untreated, a large amount of adherent moss was observed with the naked eye, and in the case of the washing solution 9, most of the attaching moss was removed, but some remained with the naked eye, and in the case of the washing solution 3 Adherent moss was almost removed and was not observed visually.

Experimental Example 3 (Experiment Using Algae Solution)

As a result of Experimental Example 1 and Experimental Example 2, the algae removal test in the solution was performed using the cleaning solution 3 having the highest cleaning power and excellent adhesion moss removal effect. 4 ml of washing solution 3 was added to 40 ml of the algae solution, and the change of the solution was photographed after one hour.

Referring to FIG. 5, after 1 hour, it was confirmed that most of the algae present in the solution were decomposed.

Claims

100 parts by weight of organic acid; And

1 to 10 parts by weight of dodecylglycerol polyethoxylate represented by the following formula (1).

Formula 1

The method according to claim 1,

The organic acid is 100 parts by weight of citric acid, 5 to 15 parts by weight of ascorbic acid, 70 to 180 parts by weight of glycolic acid and 70 to 180 parts by weight of gluconic acid, the water tank washing liquid.

The method according to claim 2,

The organic acid is a reservoir cleaning liquid, characterized in that further comprises 10 to 30 parts by weight of oxalic acid compared to 100 parts by weight of citric acid.

The method according to claim 1,

Reservoir cleaning liquid comprising a dodecylglycerol.