KR100686326B1 - Biodegradable antifoam composition and preparation method thereof - Google Patents

Abstract

A biodegradable antifoaming agent which clears demerits of an existing inorganic antifoaming agent, exhibits improved antifoaming force such as foam-breaking force and foam-inhibiting force, and is suitably used in a water treatment process is provided. A composition for biodegradable antifoaming agent used in a water treatment process comprises 0.1 to 2 weight parts of polyethyleneglycol alkylester and 0.1 to 10 weight parts of seal oil based on 100 weight parts of fatty acid ester represented by a formula 3, R-COO-(CH2CH2O)nCH2CH2OH, that is a product of esterification between a fatty acid represented by a formula 1, R-COOH, and polyethyleneglycol represented by a formula 2, OH-(CH2CH2O)nCH2CH2OH, wherein R is an alkyl group having 18 carbon atoms, and n is an integer of 3 to 4 as a repeating unit. A method for preparing a composition for biodegradable antifoaming agent used in a water treatment process comprises the steps of: esterifying a fatty acid represented by the formula 1 with polyethyleneglycol represented by the formula 2 in a reactor to generate fatty acid ester represented by the formula 3; and adding 0.1 to 2 weight parts of polyethyleneglycol alkylester and 0.1 to 10 weight parts of seal oil to 100 weight parts of the fatty acid ester.

Description

Biodegradable antifoam composition and its preparation method {Antifoaming-agent composition for water treatment process and preparation

The present invention relates to an antifoaming agent, and more particularly, to a biodegradable antifoaming agent composition for removing bubbles generated in various water treatment processes and a method of manufacturing the same.

When washing with detergent, washing your hair with shampoo, etc., you will come in contact with various forms of foam in your daily life. Industrially, it often occurs in the chemical industry, textile industry, paper industry, wastewater treatment, cooling water discharged from nuclear power plants, etc., and these bubbles are the obstacles to the industrial manufacturing process and the natural midnight disturbances as the source of environmental pollution. Should be.

Foam is defined as the dispersion of gases present in a liquid. Foaming factors that occur in the manufacturing process of each industry are blending, emulsifying, mixing, pumping, scrubbing, cleaning, temperature change, organic matter Reactions, mechanical movements that are essential in a variety of processes, and continuous mechanical movements cause foaming, and the shape and amount of foam are directly affected by this.

Methods of removing bubbles include mechanical antifoaming. There are three methods, thermal antifoaming and chemical antifoaming. Mechanical and thermal removal methods are specially used when it is difficult to change chemical and physical conditions, but they are not widely used because they do not have the fundamental protection against foaming and excessive facility and operating costs. Defoamer is the most widely used defoaming method, and the chemical defoamer is a special chemical that is added to suppress the foaming or to remove the generated foam.

The function of the antifoaming agent can be divided into the foaming function and the suppression function. The foaming function refers to the rapid destruction of the foam, and the suppression function refers to the function of preventing the reformation of the destroyed foam. Generally, antifoaming agent is called antifoaming agent without distinguishing defoamer and suppressor.

Most of the industrial defoamers are inorganic defoamers based on silicone oil. Silicone antifoaming agent is an artificially synthesized product which does not exist in nature in which organic group silicon (organosilicone) and oxygen are chemically bonded and is a chemical product that has a side chain in an alkyl group and is difficult to biodegrade.

Silicone oil is harmless and nontoxic, but when the organic silicon material contained in organosilicone antifoaming agent used in industrial process or waste water purification accumulates in the sea or rivers, it prevents the dissolution of air in the water, making it difficult for aquatic organisms to survive due to lack of dissolved oxygen. Midnight power is hindered. And if this phenomenon continues, it will rot due to lack of oxygen.

Therefore, the present invention is to solve the disadvantages of the existing inorganic antifoaming agent and to exhibit an improved antifoaming (foaming, suppression), and to provide a biodegradable antifoaming agent suitable for use in water treatment process as a technical problem.

In order to solve the above problems, the present inventors have a hydrophobic alkyl group having 18 carbon atoms, which is easy to use among organic materials, does not have a negative effect on the process, has no change in quality even when stored for 6 months or more, and has excellent processing capacity per unit price. The present invention has been completed by studying an antifoaming agent as a raw material.

According to the present invention, 0.1 to 2 parts by weight of polyethylene glycol alkyl ester and 0.1 to 10 parts of seal oil based on 100 parts by weight of a fatty acid ester of Formula 3 which is an esterification reaction product of a fatty acid of Formula 1 with polyethylene glycol of Formula 2 An antifoam composition for use in a water treatment process containing parts by weight is provided.

R-COOH

R is an alkyl group having 18 carbon atoms.

OH- (CH _{2 -} CH ₂ O) _n CH ₂ CH ₂ OH

N is an integer of 3 to 4 as a repeating unit.

R-COO-(CH _{2 -} CH ₂ O) _n CH ₂ CH ₂ OH

Wherein R is an alkyl group having 18 carbon atoms and n is an integer of 3 to 4 as a repeating unit.

In addition, according to the present invention, as a preferred method for preparing the biodegradable antifoam composition, a step of esterifying a fatty acid of Formula 1 and polyethylene glycol of Formula 2 in a reactor to produce a fatty acid ester of Formula 3, the fatty acid ester A method for producing a biodegradable antifoam composition for use in a water treatment process comprising adding 0.1 to 2 parts by weight of polyethylene glycol alkyl ester and 0.1 to 10 parts by weight of seal oil based on 100 parts by weight. Is provided.

Hereinafter, the present invention will be described in more detail.

The biodegradable antifoam composition according to the present invention contains a fatty acid ester of Formula 3, polyethylene glycol alkyl ester as an additive for improving dispersibility, and seal oil as an additive for improving defoaming power. The blending ratio of the three components in the present composition is suitably 0.1 to 2 parts by weight of polyethylene glycol alkyl ester and 0.1 to 10 parts by weight of seal oil based on 100 parts by weight of fatty acid ester of the formula (3).

The fatty acid ester of formula (3), which is a defoaming component, which is a main function of the antifoaming agent composition, is an esterification reaction product of a fatty acid of formula (1) and polyethylene glycol of formula (2), and the above two reactants are reacted by a conventional esterification method by adding a reactor. You can get it. The obtained fatty acid ester of the formula (3) was tested for the foam generated during the wastewater treatment process, it was confirmed that not only excellent antifoaming activity but also excellent biodegradability has the effect of preventing environmental pollution, a problem of the conventional antifoaming agent. Although not particularly limited, the above esterification reaction is facilitated by the addition of paratoluenesulfonic acid, and it is preferable to add silicone oil to prevent the reactants from boiling over in the reactor. At this time, the paratoluic acid and silicon oil present in the reaction product in the reactor may be separated and removed, or may be used in the present composition as they are.

Polyethylene glycol alkyl ester added as a small component in the antifoaming agent composition increases the fatty acid ester of the antifoaming component of the antifoaming agent during the antifoaming treatment, and seal oil promotes the antifoaming effect of the fatty acid ester of the general formula (3).

Features and other advantages of the present invention as described above will become more apparent from the following examples. However, the present invention is not limited to the following examples.

Example 1

70.23 g of soybean fatty acid as fatty acid of Formula 1, 25.83 g of polyethylene glycol 200 (PEG 200) as polyethylene glycol of Formula 2, 0.51 g of paratoluenesulfonic acid, and 0.07 g of silicone oil (KF-96 of Shin-Etsu Silicone Co., Ltd.) Into the tank, the reaction tank under atmospheric pressure was gradually heated while stirring. When the internal temperature of the reaction tank reached 160 ° C., the heating was stopped and the reaction was continued for 3 hours. As a result, an ester reaction product and a reaction water of fatty acid and polyethylene glycol were produced, and the reaction water in the vapor state was discharged to the liquid reaction water through the condenser through which the cooling water was circulated, and the reaction product remaining in the reaction tank was cooled using the cooling water. The reaction temperature was cooled to about 90 ° C.

0.67 g of polyethylene glycol alkyl ester [(C ₂ H ₄ O) ₃ C ₁₈ H ₃₄ O ₂ ] was added as an additive to increase the dispersibility in the reaction product, and 2.69 g of seal oil was added as an additive for improving the defoaming power. 92 g of a liquid biodegradable antifoam composition was prepared.
Here, the seal oil used is a known seal oil extracted from the seal which is a sea animal.

* Vesicle and suppressor evaluation

Anti-foaming property: 80 g of phosphite or 49 g of water was put into a mass cylinder of 6 cm in diameter and 30 cm in height, and then prepared in advance while decomposing acid (85% phosphoric acid 120g + 98% sulfuric acid 86g) while stirring at 95 ° C (stirring speed 300rpm, stirring blade diameter 4.5cm). ) Was added dropwise and subjected to decomposition foaming, and then 0.32 g of the antifoam composition of Example 1 was added dropwise to measure the height of one surface with respect to the elapsed time after the dropping, and the antifoaming property was determined. The results are shown in Table 1.

Anti-foaming property: The antifoam composition of Example 1 was added dropwise while 80 g of phosphorite and 49 g of water were added to a mass cylinder having a diameter of 6 cm and a height of 30 cm, followed by stirring at 95 ° C. (stirring speed 300 rpm, stirring blade diameter 4.5 cm), and then prepared in advance. After decomposing acid (120 g of 85% phosphoric acid + 86 g of 98% sulfuric acid) was added, the height of one surface was measured with respect to the elapsed time, and the inhibition was obtained. The results are shown in Table 1.

Elapsed time (minutes) Antifoam (mm) Suppression (mm) 0 280 240 30 240 240 60 240 250 90 240 250 120 240 260 150 240 260 180 240 260 210 240 260 240 240 270 270 240 270 300 240 270

 The antifoaming and suppressing test results show an antifoaming effect of at least 1.5 times and up to 3 times as compared to the existing antifoaming agents.

* Biodegradation Experiment

Biodegradation experiments were carried out in a number of reactors with a maximum volume of 7 liters in a constant temperature room maintained at 20 ° C. and equipped with a stirring mixer and an air pump. In the experiment, the mixer for mixing the sludge was operated at 80 rpm to allow the sludge to operate uniformly without sinking, and the air injection amount was 30 mL / min.

The sludge was used for aeration tank sludge of the Korea Environmental Management Corporation. The sludge was washed five times to remove dissolved or adsorbed substrate. In each reactor, the antifoamer composition of Example 1 was diluted 100-fold, 200-fold, 500-fold, and 1000-fold, and each 100 mL was added to 5 liter of activated sludge. At this time, the defoaming agent composition concentration of each reactor was 0.2, 0.1, 0.04, 0.02 ppm, respectively.

Sampling and analysis were performed at 0, 0.5, 1, 2, 3, 6, and 12 days. The analysis items were SCOD concentration and removal rate, and TOC concentration and removal rate. The measurement results are shown in Tables 2-5.

Aeration time (days) SCOD concentration (mg / L) Dilution ratio 1000 Dilution Ratio 500 Dilution ratio 200 Dilution Ratio 100 0 13.3 19.1 24.6 44.9 0.5 13.2 18.9 23.6 44.1 One 12.9 15.9 20.7 40.6 2 12.9 15.2 18.3 39.7 3 12.2 16.3 18.7 38.8 4 12.6 15.9 16.1 31.5 6 10.6 13.3 14.6 15.2 12 11.2 9.2 10.4 11.4

Aeration time (days) SCOD removal rate (%) Dilution ratio 1000 Dilution Ratio 500 Dilution ratio 200 Dilution Ratio 100 0 0.0 0.0 0.0 0.0 0.5 0.8 1.0 3.3 1.8 One 3.0 16.8 15.9 9.6 2 3.0 20.3 25.6 11.6 3 8.3 14.9 32.1 14.1 4 5.3 16.7 34.6 29.9 6 20.3 30.5 40.6 60.1 12 15.6 51.7 57.6 74.6

Aeration time (days) TOC concentration (mg / L) Dilution ratio 1000 Dilution Ratio 500 Dilution ratio 200 Dilution Ratio 100 0 6.5 10.8 15.0 23.9 0.5 6.3 10.6 13.2 22.7 One 6.1 6.8 9.9 21.2 2 5.5 5.7 8.9 18.9 3 5.4 5.7 7.5 17.2 4 5.3 5.9 6.0 13.5 6 5.1 5.3 6.0 6.8 12 3.6 3.1 5.1 4.2

Aeration time (days) TOC removal rate (%) Dilution ratio 1000 Dilution Ratio 500 Dilution ratio 200 Dilution Ratio 100 0 0.0 0.0 0.0 0.0 0.5 3.1 1.9 12.0 5.0 One 6.2 37.0 34.0 11.3 2 15.5 47.3 40.7 20.8 3 16.9 47.4 50.0 28.1 4 18.5 45.3 60.0 43.3 6 21.5 51.2 60.1 71.6 12 44.6 71.0 66.2 82.6

The reduction in SCOD is the difference between the substrate COD, which is the last biodegradable of the initial lipid COD, and can be classified as an organic substance that is easy to degrade. Table 2 shows the SCOD change in the batch reactor when the dilution ratio was adjusted to 100 to 1000, Table 3 shows the SCOD removal rate. For 12 days, SCOD reduction was 74.6% for dilution ratio of 100 times, 57.6% for 200 times, 51.7% for 500 times, and 15.8% for 1000 times. Tables 4 and 5 show the TOC concentration and removal rate according to the aeration time, showing a similar tendency to SCOD, and the removal rate was higher than that of SCOD.

From the above experimental results, it can be seen that the biodegradable antifoam composition of the present invention exhibited better biodegradability than the OECD environmental standard (without paraffin hydrocarbon and at least 60% of the substance must be biodegraded within 30 days).

As described above, the biodegradable antifoaming agent composition according to the present invention is a non-silicone antifoaming agent, which has excellent biodegradability and quickly removes bubbles generated in the water treatment process, thereby shortening the water treatment time, and there is no change in quality even in long-term storage and processing per unit price. There are advantages such as excellent ability.

Claims (3)

For use in a water treatment process containing 0.1 to 2 parts by weight of polyethylene glycol alkyl ester and 0.1 to 10 parts by weight of seal oil based on 100 parts by weight of a fatty acid ester of Formula 3, which is an esterification reaction of a fatty acid of Formula 1 with polyethylene glycol of Formula 2 Biodegradable antifoam composition for: [Formula 1] R-COOH [Formula 2] OH- (CH _{2 -} CH ₂ O) _n CH ₂ CH ₂ OH [Formula 3] R-COO-(CH _{2 -} CH ₂ O) _n CH ₂ CH ₂ OH In Formulas 1, 2 and 3, R is an alkyl group having 18 carbon atoms, and n is an integer of 3 to 4 as a repeating unit. In preparing the antifoaming agent composition according to claim 1, the step of esterifying a fatty acid of Formula 1 and polyethylene glycol of Formula 2 to produce a fatty acid ester of Formula 3 in a reactor, based on 100 parts by weight of the fatty acid ester A method for producing a biodegradable antifoam composition for use in a water treatment process comprising adding 0.1 to 2 parts by weight of glycol alkyl ester and 0.1 to 10 parts by weight of seal oil. 3. The method for producing a biodegradable antifoam composition for use in a water treatment process according to claim 2, wherein paratoluenesulfonic acid and silicone oil are added as a reaction additive during the esterification reaction.