JP2005169271A - Antifoaming agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifoaming agent which has both of strong initial foam destruction ability and foam suppression ability, is capable of continuously repeating the suppression of foaming and the destruction of bubbles, does not hinder microbial waste water disposal activity and is suitable for defoaming of an aqueous foaming solution. <P>SOLUTION: The oil in water type emulsion antifoaming agent composition consists of oil-soluble metallic soap, a solvent and water. Therein, the solvent comprises one kind or two kinds or more selected from animal and plant fat and oil, mineral oil, an aliphatic acid and ester of the aliphatic acid of carbon number of 10-30, a hydrocarbon of carbon number of 10-30 and higher alcohol of carbon number of 10-30. The oil in water type emulsion antifoaming agent composition is made by mixing a solution which is formed by dissolving the oil-soluble metallic soap of 0.001 to 20 pts.wt. into the solvent of 100 pts.wt. with emulsifier and water and emulsifying the mixture. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an emulsion-based antifoaming agent composition. More specifically, the present invention relates to an emulsion-based antifoaming agent composition that can suppress the generation of bubbles and effectively erase the generated bubbles in various production processes, wastewater treatment processes, sewage treatment processes, and the like.

Conventionally, bubbles generated in various manufacturing process water, drainage, sewage treatment, etc. have an adverse effect on production efficiency and environmental problems, and various defoaming treatments have been performed. For example, an amide antifoaming agent is a fatty acid amide dispersed as fine particles in mineral oil, and has a strong antifoaming action while being relatively inexpensive, so that it can be used in general wastewater and the like in the paper industry. Widely used. This strong defoaming effect is exerted by the diffusion of fatty acid amide fine particles having a defoaming action to the surface of the dispersion medium, and the mineral oil as the dispersion medium is extremely useful as a carrier for diffusing the fatty acid amide fine particles to the surface. It is important. However, oil-based ones such as antifoaming agents have a drawback that they cannot be used for microbial wastewater treatment or the like because of microbial activity inhibition.
Further, a composition (Patent Document 1) containing fine particles such as solid fatty acid amide as a defoaming component by a water-in-oil emulsion composed of mineral oil and water is also used. An inevitable problem occurs.
In order to avoid such difficulties, an oil-in-water emulsion defoamer is desirable, and an oil-in-water emulsion defoamer mainly composed of silicone, fatty acid, higher alcohol, polyether, etc. Although used, there is a drawback that the defoamer titer does not reach that of the fatty acid amide system. Although it is desirable that the fatty acid amide can be an oil-in-water emulsion defoamer, the fatty acid amide has a drawback that it cannot stably form an oil-in-water emulsion.
Japanese Patent Laid-Open No. 2002-143606

  The present invention has both stronger initial foaming and foam suppression than conventional oil-in-water emulsion antifoaming agents, and can continuously suppress foaming and destroy foam, thereby inhibiting microbial wastewater treatment activity. The object of the present invention is to provide an antifoaming agent suitable for the defoaming treatment of a water-based foaming solution that is not performed.

As a result of diligent research using a metal soap having a high defoaming titer and making it an oil-in-water emulsion defoamer, the present inventors have found that in a specific solvent that can dissolve the oil-soluble metal soap. It was found that the above-mentioned problems can be solved by dissolving the oil-soluble metal soap in a specific ratio and adding water thereto to emulsify, and the present invention has been completed based on this finding.
That is, the present invention
(1) In an oil-in-water emulsion defoamer composition comprising an oil-soluble metal soap, a solvent and water, the solvent is an animal or vegetable oil or fat, mineral oil, a fatty acid having 10 to 30 carbon atoms, the fatty acid ester, carbon 1 type or 2 types or more selected from hydrocarbons of several tens to thirty and carbons having ten to thirty carbons, and 0.001 to 20 parts by weight of the oil-soluble metal soap in 100 parts by weight of the solvent An oil-in-water emulsion defoamer composition, wherein the dissolved solution is emulsified by mixing with an emulsifier and water,
(2) The oil-in-water emulsion defoamer composition according to item 1, wherein the oil-soluble metal soap is aluminum stearate,
(3) The oil-in-water emulsion defoamer composition according to item 2, wherein 0.001 to 12% by weight of aluminum stearate is contained in the defoamer composition, and
(4) One or more selected from animal and vegetable oils and fats, mineral oil, fatty acids having 10 to 30 carbon atoms, fatty acid esters, hydrocarbons having 10 to 30 carbon atoms and higher alcohols having 10 to 30 carbon atoms An oil-in-water emulsion defoamer composition obtained by mixing 0.001 to 20 parts by weight of an oil-soluble metal soap with 100 parts by weight of a solvent, an emulsifier and water, and a fatty acid amide dispersed therein An antifoam composition characterized by being added to and mixed with a mineral oil and emulsified,
Is to provide.

 If the antifoam composition of the present invention is used, the performance is dramatically improved as compared with the conventional emulsion antifoam composition, and the defoamer composition necessary for achieving the same effect can be reduced. It can contribute to reduction of environmental load and reduction of processing costs. In addition, it can be widely used as an emulsion-based antifoaming agent that can eliminate foams generated in various manufacturing process water, wastewater, sewage treatment equipment, etc. without hindering microbial treatment activity. Furthermore, according to the defoamer composition of the present invention, the activated fatty acid amide can be dispersed in mineral oil and contained in the oil-in-water emulsion defoamer composition. Goods can be used without the application of dangerous goods by the Fire Service Act.

The oil-soluble metal soap used in the present invention can be used without any particular limitation on the oil-soluble organic acid non-alkali metal salts that can be dissolved in the solvent used in the present invention. For example, an aluminum salt, calcium salt, magnesium salt, cobalt salt or the like of a saturated or unsaturated fatty acid or alicyclic organic acid can be used. Examples of fatty acid or alicyclic organic acid that can be suitably used for the oil-soluble metal soap used in the present invention include myristic acid, palmitic acid, stearic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, linol. Examples thereof include acid, linolenic acid, soybean fatty acid, coconut fatty acid, and naphthenic acid. These fatty acids or alicyclic organic acids can be used alone, or in combination of two or more, can be used as non-alkali metal chlorides and used as oil-soluble metal soaps used in the present invention. .
As the oil-soluble metal soap used in the present invention, stearic acid, or an aluminum salt of oleic acid or soybean fatty acid can be particularly preferably used.
As the aluminum stearate used as the oil-soluble metal soap used in the present invention, those commercially obtained and commercially available can be used in addition to pure products. As the industrially obtained and commercially available aluminum stearate, a mixture of three types of aluminum salts of mono-, di- and tri-stearic acids can be suitably used. The aluminum stearate used in the present invention can be used without any particular limitation on the mixing ratio of the three types of aluminum salts. The industrial aluminum stearate used in the present invention has a melting point lower than that of pure aluminum stearate and is much cheaper, and can be particularly suitably used as the oil-soluble metal soap used in the present invention.
The oil-soluble metal soap used in the present invention can be used by dissolving 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, in 100 parts by weight of the solvent used in the present invention. When the amount is less than 0.001 part by weight, the defoaming performance is insufficient, and when the amount exceeds 20 parts by weight, the emulsion formability is poor.
As the oil-soluble metal soap used in the present invention, one in which aluminum stearate is contained in an antifoaming agent composition by 0.001 to 12% by weight can be particularly preferably used.

The solvent used in the present invention is an oil-based solvent having a melting temperature lower than the atmospheric boiling point of 100 ° C. and capable of dissolving the oil-soluble metal soap used in the present invention, and the solution in which the oil-soluble metal soap is dissolved is an emulsifier. And those that can form an oil-in-water emulsion when mixed with water.
The solvent used in the present invention is an animal or vegetable oil or fat, mineral oil, a fatty acid having 10 to 30 carbon atoms, or a fatty acid ester thereof, a hydrocarbon having 10 to 30 carbon atoms, or a carbon number 10 to 10 Thirty higher alcohols can be used. A solvent composed of one or more of these solvents can be used.
As animal and vegetable oils and fats used in the present invention, vegetable oils and animal oils from the natural world can be used. Examples of oils and fats that can be used include soybean oil, palm oil, olive oil, rapeseed oil, sesame oil, and the like. Moreover, fish oil, beef tallow, pork tallow, sheep oil tallow etc. can be used as animal oil.
The mineral oil used in the present invention is obtained from refining, fractionation, separation residue oil, etc. of minerals such as petroleum and coal, and is widely used in solvents and industrial raw materials because it is supplied in large quantities and is inexpensive. Yes. As the mineral oil used in the present invention, a commercially available mineral oil having a melting temperature lower than 100 ° C. can be used without particular limitation. For example, paraffin oil, naphthenic oil, naphtha, kerosene, light oil, spindle oil, high boiling point oil and the like can be used. As the mineral oil used in the present invention, a hydrocarbon mixture having 10 to 30, preferably 12 to 28 carbon atoms can be suitably used. Those having less than 10 carbon atoms have a large evaporation loss, and those having more than 30 have poor emulsion forming properties.
As the fatty acid used in the present invention, a saturated or unsaturated fatty acid can be used. Myristic acid, palmitic acid, stearic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, soybean fatty acid, coconut fatty acid and the like can be used. These fatty acids can be used individually by 1 type, and can also be used in combination of 2 or more type. As the fatty acid used in the present invention, a fatty acid having 10 to 30, preferably 12 to 28 carbon atoms can be used. Those having less than 10 carbon atoms have insufficient dissolving power, and those having more than 30 have poor emulsion forming properties.
The fatty acid ester used in the present invention is a condensation product of the fatty acid and alcohol used in the present invention, and the fatty acid ester used in the present invention has a total carbon number of 10 to 30, preferably 12 to 12, of the fatty acid and alcohol. 28 fatty acid esters can be used. Those having less than 10 carbon atoms have insufficient dissolving power, and those having more than 30 have poor emulsion forming properties.

As the hydrocarbon used in the present invention, a saturated or unsaturated aliphatic or alicyclic hydrocarbon having 10 to 30 carbon atoms, preferably 12 to 28, an alkyl group-added aromatic hydrocarbon, or the like can be used. Those having less than 10 carbon atoms have a large evaporation loss, and those having more than 30 have poor emulsion forming properties.
Examples of the hydrocarbon used in the present invention include decane, dodecane, dodecylbenzene, polyethylene oligomer, polypropylene oligomer, polybutadiene oligomer, and polyethylene / propylene copolymer oligomer. These hydrocarbons can be used individually by 1 type, and can also be used in combination of 2 or more type.
As the higher alcohol used in the present invention, a saturated or unsaturated aliphatic or alicyclic alcohol having 10 to 30, preferably 12 to 28 carbon atoms can be used. Those having less than 10 carbon atoms have large evaporation loss and insufficient dissolving power, and those having more than 30 carbon atoms have poor emulsion forming properties. As the higher alcohol used in the present invention, for example, stearyl alcohol, behenyl alcohol, dodecyl alcohol and the like can be used. These aliphatic alcohols can be used alone or in combination of two or more.
The emulsifier used for this invention can be used without restrict | limiting especially a well-known emulsifier. Anionic, cationic, amphoteric and nonionic surfactants can be used. These surfactants can be used individually by 1 type, and can also be used in combination of 2 or more type. For example, sorbitan monooleate [Toho Chemical Co., Ltd., PAS-80], polyoxyalkylene alkyl ether [Nikka Chemical Co., Ltd., Sunmole DB-60] and the like can be suitably used.
The emulsifier used in the present invention can appropriately use an auxiliary agent in order to further enhance the effect. For example, polyoxyalkyl ether [Nippon Catalyst, Softanol 90], polyoxyalkyl ether [Nippon Catalyst, Softanol 120], and the like can be suitably used.
If the water used for this invention is the water which filtered the foreign material with neutral water, it can be used without restrict | limiting especially distilled water, city tap water, well water, etc.
As the fatty acid amide used in the present invention, those known as an antifoaming agent can be used without particular limitation. For example, stearic acid amides, oleic acid amides and the like can be preferably used.
The fatty acid amide used in the present invention can be dispersed and suspended in the oil layer using a known method without any particular limitation. The fatty acid amide used in the present invention can be particularly preferably used by being dispersed and suspended in the mineral oil used in the present invention.
The composition in which the fatty acid amide used in the present invention is dispersed and suspended in the mineral oil used in the present invention can be well mixed with the oil-in-water emulsion defoamer composition of the present invention. A water-in-water hybrid emulsion antifoam composition can be formed. According to the present invention, the problem of solid fatty acid amide fine particles in a water-in-oil emulsion that separates and settles during storage, which is a drawback of the conventional fatty acid amide dispersion antifoam composition, can be solved.

The oil-in-water emulsion defoamer composition of the present invention is a liquefied product by heating a specific solvent capable of dissolving the oil-soluble metal soap used in the present invention above its melting point, and this is used for the oil-soluble metal used in the present invention. A predetermined amount of soap is dissolved, and an emulsifier and an auxiliary agent are added to this solution, and a predetermined amount of water is added to and mixed with the solution, followed by emulsification into an oil-in-water type.
The fatty acid amide-dispersed mineral oil-containing oil-in-water emulsion defoamer composition of the present invention comprises the fatty acid amide used in the present invention dispersed and contained in the mineral oil used in the present invention, The oil-in-water emulsion defoamer composition of the present invention can be mixed to obtain an oil-in-water type or water-in-oil type mixed emulsion.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Defoaming performance comparison test The target water for the defoaming test was 1.5 L of an aqueous solution containing 25 ppm of a nonionic surfactant [Nikka Chemical Co., Ltd., Sunmol DB-80]. Antifoam test water was prepared by adding 5 ppm of the antifoam composition prepared in each of the examples and comparative examples to this aqueous solution. In the defoaming performance comparison test, this defoaming test water is put in a cylindrical glass container having an inner diameter of 30 cm, and the defoaming test water surface is raised at a circulation rate of 5 L / min using a pump vertical circulation type defoaming tester. The water was continuously circulated and dropped from the position of 40 cm onto the water surface for 6 minutes, and then allowed to stand for 3 minutes. Thereby, the bubble-breaking property and the foam-suppressing property at the time of circulation were compared with the bubble-breaking property at rest.
Preparation of antifoam composition The antifoam composition used for the above defoaming performance comparison test was prepared according to the following examples and comparative examples.
Example 1
20 g of stearic acid [Tokyo Kasei Co., Ltd., SA-400] was placed in a reaction vessel equipped with a stirrer with an internal volume of 0.3 L, heated to 75 ° C. and melted, and industrial aluminum stearate [Tokyo Kasei ( Co., Ltd., SA-1000] was added and stirred, and further heated to 90 ° C. to completely dissolve the aluminum stearate. To this solution was added 1 g of emulsifier sorbitan monooleate [Toho Chemical Co., Ltd., PAS-80] and auxiliary polyoxyalkyl ether [Nippon Catalyst Co., Ltd., Softanol 90] 2 g. While maintaining the liquid temperature at 80 ° C., with stirring, water was gradually added and mixed so that the total amount became 100 g to obtain a uniform liquid phase. This liquid was cooled to room temperature to obtain 100 g of an oil-in-water emulsion defoamer composition.

Example 2
The procedure was the same as in Example 1 except that stearic acid was replaced with oleic acid and aluminum stearate was added at 40 ° C.
Example 3
The procedure was the same as in Example 1, except that stearic acid was replaced with palmitic acid and aluminum stearate was added at 70 ° C.
Example 4
The procedure was the same as in Example 1 except that stearic acid was replaced with soybean oil and aluminum stearate was added at 60 ° C.
Example 5
The procedure was the same as in Example 1 except that stearic acid was replaced with rapeseed oil and aluminum stearate was added at 60 ° C.
Example 6
The procedure was the same as in Example 1 except that the amount of stearic acid was changed to 15 g and spindle oil 5 g was added.
Example 7
The procedure was the same as in Example 1 except that the amount of stearic acid was changed to 15 g and 5 g of castor oil was added.
Example 8
The procedure was the same as in Example 1, except that stearic acid was replaced with methyl stearate and aluminum stearate was added at 60 ° C.
Example 9
An oil-in-water emulsion defoamer composition was prepared under the same conditions as in Example 1 except that the amount of stearic acid was changed to 15 g and tallow 5 g was added. Separately, 10 g of stearamide powder [Nippon Kasei Co., Ltd., Sripack] was added to 70 g of mineral oil [Nippon Petroleum Corporation, Neutral 150], and 80 g of fatty acid amide dispersed mineral oil dispersed by stirring. Was prepared. To this was added 20 g of the oil-in-water emulsion defoamer composition described above and mixed with stirring to prepare 100 g of an oil-in-water emulsion antifoam composition-containing fatty acid amide-dispersed mineral oil defoamer.
Example 10
The procedure was the same as in Example 1 except that stearic acid was replaced with stearyl alcohol and aluminum stearate was added at 60 ° C.

Example 11
It carried out on the same conditions as Example 1 except having replaced the industrial aluminum stearate with calcium stearate.
Example 12
The same conditions as in Example 1 were followed except that the industrial aluminum stearate was replaced with magnesium stearate.
Example 13
It carried out on the same conditions as Example 1 except having changed the industrial aluminum stearate to calcium oleate.
Example 14
The same conditions as in Example 1 were followed except that the industrial aluminum stearate was replaced with barium stearate.
Example 15
The sorbitan monooleate sorbitan was replaced with sorbitan sesquioleate [Daiichi Pharmaceutical Co., Ltd., Sorgen-30], and the auxiliary polyoxyalkyl ether was replaced with polyoxyalkylene alkyl ether [Nika Kagaku Co., Ltd., Sanmor DB-80] ] Was performed under the same conditions as in Example 1, except that
Example 16
Emulsifier sorbitan monooleate [Toho Chemical Industries, Ltd., PAS-80] is replaced with sorbitan monooleate [Toho Chemical Industries, Ltd., S-80], and auxiliary polyoxyalkyl ether is replaced with polyoxyethylene monooleate The test was performed under the same conditions as in Example 1 except that [Nika Kagaku Co., Ltd., NN200MN] was used.
Comparative Examples 1-16
From each example of Examples 1-16, the oil-soluble metal soap used for each was removed, water was added so that the total amount would be 100 g, and the oil-in-water type corresponding to each example of Examples 1-16 An emulsion composition was prepared and used as an oil-in-water emulsion type antifoaming composition of Comparative Examples 1 to 16 corresponding to Examples of Examples 1 to 16.
The result of the defoaming performance comparison test of Examples 1-16 is shown in Table 1, and the result of the defoaming performance comparison test of Comparative Examples 1-16 is shown in Table 2.

  As can be seen in Tables 1 and 2, the water to which the emulsion antifoam composition of Examples 1-16 containing 1% by weight of oil-soluble metal soap was added was the amount of foam both during circulation and after resting There are few, and it turns out that it is excellent in the effect which prevents generation | occurrence | production of a bubble, and a defoaming effect. Water to which the emulsion antifoaming compositions of Comparative Examples 1 to 16 containing no oil-soluble metal soap are added has a large amount of foam both during circulation and after standing still.

  Since the emulsion antifoaming composition of the present invention has strong initial foam breaking property and foam inhibiting property, it can be utilized without impairing the activity of microorganisms in biological wastewater treatment and the like.

Claims (4)

  In an oil-in-water emulsion defoamer composition comprising an oil-soluble metal soap, a solvent, and water, the solvent is an animal or vegetable oil or fat, mineral oil, a fatty acid having 10 to 30 carbon atoms, the fatty acid ester, or 10 to 10 carbon atoms. A solution comprising one or more selected from 30 hydrocarbons and higher alcohols having 10 to 30 carbon atoms, wherein 0.001 to 20 parts by weight of the oil-soluble metal soap is dissolved in 100 parts by weight of the solvent. Is mixed with an emulsifier and water to give an emulsion, which is an oil-in-water emulsion defoamer composition.   2. The oil-in-water emulsion antifoam composition according to claim 1, wherein the oil-soluble metal soap is aluminum stearate.   The oil-in-water emulsion defoamer composition according to claim 2, wherein 0.001 to 12% by weight of aluminum stearate is contained in the defoamer composition.   Solvent 100 comprising one or more selected from animal and vegetable oils and fats, mineral oil, fatty acids having 10 to 30 carbon atoms, fatty acid esters, hydrocarbons having 10 to 30 carbon atoms and higher alcohols having 10 to 30 carbon atoms Mineral oil in which an oil-in-water emulsion type antifoaming agent composition obtained by mixing 0.001 to 20 parts by weight of an oil-soluble metal soap with an emulsifier and water is mixed with a fatty acid amide in a weight part. An antifoam composition characterized by being added to, mixed and emulsified.