JP3162593B2 - W / O emulsion type defoamer composition and defoaming method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a W / O emulsion type antifoaming composition. More specifically, W / is suitable as a defoaming agent for a pulp manufacturing process, a fiber manufacturing / processing process, or a wastewater treatment process, which is excellent in defoaming performance, provides a large defoaming effect with a small amount of addition, and has excellent emulsion stability. The present invention relates to an O emulsion type antifoaming composition.

[0002]

2. Description of the Related Art Silicone antifoaming agents have various excellent properties as compared with other types of antifoaming agents, and thus are suitable for use in foaming industries such as the chemical, food, petroleum, textile, and pharmaceutical industries. Although widely used, many are O /
It is a W emulsion type.

An O / W emulsion type silicone defoamer is obtained by emulsifying an organopolysiloxane composition or the like obtained by dispersing a finely divided inorganic filler such as silica, titanium dioxide or aluminum oxide in an organopolysiloxane. It is known. Since the defoaming performance and acid / alkali resistance of this type of defoaming agent are mainly determined by the properties of the organopolysiloxane composition, improvement of the defoaming performance is focused on the modification of the organopolysiloxane composition. ing.

Conventionally, as an O / W emulsion type silicone antifoaming agent, a composition obtained by treating an organopolysiloxane composition comprising an organopolysiloxane and silica with a nitrogen-containing organosilicon compound is emulsified to improve the defoaming performance. An enhanced one (JP-B-51-35556), an emulsion of a composition obtained by adding an organohydrogenpolysiloxane, silica and a catalyst to an organopolysiloxane (JP-A-57-48307).
There is known an emulsion of an organopolysiloxane to which an emulsifier has been added, to which a silazane-treated silica-based filler has been added (JP-A-52-2887).

Also, since organopolysiloxane has a very low surface tension, a large amount of emulsifier is used to adjust the O / W emulsion type silicone antifoaming agent, or a special emulsifying dispersant or modified organopolysiloxane is used. The point that siloxane should be used is described in JP-B-52-19836, JP-B-52-22638, JP-B-55-23084, JP-A-6-142410 and JP-A-6-142411.
It is described in each gazette.

On the other hand, as a W / O emulsion type, a composition containing a quenched amide compound (JP-A-55-703)
No. 08 publication) is known.

[0007]

The conventional O / W emulsion type silicone antifoaming agent has the disadvantage that the emulsion is destroyed under severe conditions such as high temperature, high alkalinity and high shearing force, and the defoaming performance is reduced. there were. In addition, in the case of the method of improving the stability of the emulsion by adjusting the amount of the emulsifier, when a large amount of the emulsifier is added, the emulsion is stabilized but the defoaming performance is deteriorated. As much as possible, the defoaming performance is improved, but the emulsion particles become coarse and the emulsion stability deteriorates remarkably. Therefore,
It has been extremely difficult to obtain an O / W emulsion type silicone antifoaming agent which satisfies both at the same time by this method. As described above, the conventional O / W emulsion-type silicone antifoaming agent is intended to improve any of initial foam-breaking property, foam-suppressing continuity or emulsion stability, and can simultaneously improve these three. There was nothing. In particular, in the pulp production process, the fiber production / processing process, or the wastewater treatment process, there was no one capable of achieving a sufficient initial foam breaking property and foam sustainability.

Further, the antifoaming agent comprising the composition containing the quenched amide compound is remarkably inferior in foaming sustainability, and has a disadvantage that pitch-like aggregates due to the amide compound and the like are easily generated. Since it contains a dioxin precursor, it is environmentally unfavorable.

[0009]

DISCLOSURE OF THE INVENTION The present invention has excellent initial foam breaking property, excellent foam suppression continuity and emulsion stability even under severe conditions such as high temperature, high alkali and high shearing force, and has a pitch-like agglomeration. It is an object of the present invention to provide a W / O emulsion-type defoaming agent which generates little matter and does not contain a dioxin precursor. That is, the present invention provides: Viscosity at 25 ° C. comprising organopolysiloxane and finely divided silica having a viscosity of 50 to 200,000 mPa · s.
B. 10 to 88 parts by weight of one or more organopolysiloxane compositions Emulsifier 1 to 50 parts by weight C.I. 1 to 50 parts by weight of water One or more organic solvents having a kinematic viscosity at 40 ° C. of 0.5 to 11 cSt and / or an animal or vegetable oil or / and a fatty acid ester selected from tallow fatty acid methyl and methyl oleate or / and oleic acid and isostearic acid Fatty acids 10-6 selected from
A W / O emulsion type antifoaming composition (hereinafter abbreviated as an antifoaming composition) comprising 0 parts by weight, and a defoaming method using the composition. The stability, the initial foam breaking property, and the foam suppression duration can be simultaneously solved.

The organopolysiloxane composition constituting the antifoaming composition of the present invention has a viscosity at 25 ° C. of 50 to 50.
The organopolysiloxane composition is selected from one or more of the compositions having a molecular weight of 200,000 mPa · s, and the organopolysiloxane composition is composed of an organopolysiloxane represented by the following general formula and powdered silica. R _m · Si · O _{(4-m) / 2} (where R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group, a tolyl group) Aryl groups, chloromethyl groups in which part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, polyalkylene oxides, etc., 3,3,3-trifluoropropyl groups, The same or different unsubstituted or substituted hydrocarbon groups such as a propyl group substituted by a cyanopropyl group, an addition polymer of propylene oxide and ethylene oxide, and m represents an average value of 1.9.
~ 2.1)

Examples of the organopolysiloxane include dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, polydimethylsiloxane-polydiphenylsiloxane copolymer, polymethyl-3,3,3-trifluoropropylsiloxane,
And polydimethyl-chloropropylmethylsiloxane copolymer.

The finely divided silica to be added to the organopolysiloxane may be either dry silica or wet silica, which is conventionally known as a silica filler, including precipitated silica, silica xerogel, fumed silica and fumed silica. And silica whose surface is treated with an organic silyl group. Specific examples include Aerosil (Nippon Aerosil), Nip Seal (Nippon Silica), Caboseal (Cabot), Santocell (Monsanto Chemical) and the like.

The viscosity of the organopolysiloxane composition is
It is better to be as low as possible from the viewpoint of initial foam breaking property, easy dispersibility and workability, and it is better to be as high as possible from the viewpoint of sustainability of foam suppression. Therefore, the viscosity is determined in consideration of these balances, and usually 50 to 200,000 m
Pa · s, preferably 100-100,000 mPa ·
s. When the viscosity is less than 50 mPa · s, the sustainability of the foam is significantly deteriorated. When the viscosity exceeds 200,000 mPa · s, not only the workability is deteriorated, but also the emulsification becomes difficult, and the initial foam breaking property is significantly deteriorated.

Specific examples of commercially available organopolysiloxane compositions include SC5500, SC5570 and BY28.
-503 (Toray Dow Corning Silicone), K
S66, KS69, KS67B, KS506, KS53
0, KS537 (Shin-Etsu Chemical), FS Anti-Home D
B-100, FS Anti-Home F-16, FS Anti-Home 80, FS Anti-Home 81 (Dow Corning Asia), SL, SR, S369, PULPSIL50C,
S575 (Waker Chemicals East Asia),
FZ-328, FZ-334, FZ-5603 (Nihon Unicar), TSA750, YSA6406 (Toshiba Silicone) and the like.

The amount of the organopolysiloxane composition is usually from 10 to 88 parts by weight per 100 parts by weight of the defoamer composition.
Parts by weight, preferably 30 to 60 parts by weight. If the amount is less than 10 parts by weight, the initial foam breaking performance and the foam suppressing sustainability are remarkably inferior. If the amount exceeds 88 parts by weight, the amount of the emulsifier, water, organic solvent and the like is reduced, and the emulsion stability and the initial foam breaking property are deteriorated. .

As the emulsifier, any of a nonionic type, a cationic type and an anionic type can be used, but it is preferable that the nonionic type is mainly used from the viewpoint of the stability of the W / O emulsion. For example, sorbitan fatty acid esters, sucrose fatty acid esters, glycerin fatty acid esters, higher fatty acid alkylene oxide adducts, higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, silicone-based emulsifiers (polyalkylene oxide-modified organopolysiloxane), and the like. Can be used. Specific examples include sorbitan monooleate,
Sucrose monooleate, glycerin monooleate, glycerin monostearate, polyoxyethylene sorbitan triolate, polyoxyethylene monolaurate, polyethylene glycol distearate, polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol stearyl ether, polyethylene Nonionic emulsifiers such as glycol nonylphenyl ether, dodecylbenzenesulfonic acid,
Anionic emulsifiers such as alkyl phosphate salts and cationic emulsifiers such as alkylbenzyl ammonium salts and oleylamine salts can be used. Examples of commercially available silicone emulsifiers include FZ-2130, 2171 (Nippon Unicar), SH3775C (Tore Dow Corning Silicone), KF-945A (Shin-Etsu Silicone), and the like.

The amount of the emulsifier is usually 1 to 50 parts by weight, preferably 2 to 30 parts by weight, per 100 parts by weight of the antifoaming composition. If the amount is less than 1 part by weight, an emulsion having good stability cannot be obtained. If the amount is more than 50 parts by weight, the defoaming performance is remarkably poor.

Water has the effect of reducing the flammability and improving the safety in handling, in addition to the purpose of increasing the diffusibility into the aqueous foaming liquid and improving the initial foam breakability. Distilled water, ion exchanged water,
Any of tap water, industrial water, well water, river water, spring water and the like can be used, but soft water such as tap water and industrial water is preferable.

The amount of water is usually 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the defoamer composition. If the amount is less than 1 part by weight, the diffusibility into the aqueous foaming liquid is insufficient, and the initial foam breaking property cannot be improved. If the amount is more than 50 parts by weight, the emulsion stability is poor and the defoaming performance deteriorates.

Organic solvent and / or animal or vegetable oil or /
And fatty acid esters and / or fatty acids (hereinafter abbreviated as organic solvents and the like) exhibit extremely excellent initial foam breaking performance and foam suppression sustaining performance when used in combination with the organopolysiloxane composition. Further, they contribute to adjust the viscosity of the defoamer composition which is easily influenced greatly by the viscosity of the organopolysiloxane composition to be used, and assist the emulsification of the organopolysiloxane composition with water. It is also useful for providing excellent emulsion stability with a small amount of emulsifier.

Examples of the organic solvent include aliphatic solvents, aromatic solvents, low odor solvents, odorless solvents, liquid paraffin, and lubricating oils produced from petroleum. Particularly preferred are a non-aromatic solvent containing no dioxin precursor, and liquid paraffin which has been completely hydrorefined. Specifically, No. 0 Solvent L, No. 0 Solvent H, AF Solvent 4 (Nippon Oil), Pure Rex 7, Christol 52, (Esso Petroleum), Liquid Paraffin 40-S (Sanko Chemical Industry), Diana Solvent L
A25 (Idemitsu Kosan).

The kinematic viscosity of the organic solvent at 40 ° C. is 0.5
１１11 cSt. If it is less than 0.5 cSt, the organic solvent is liable to volatilize, the emulsion stability is deteriorated due to the volatilization, the viscosity becomes high, and the handleability and the sustainability of foam suppression deteriorate. If it is higher than 11 cSt, it is difficult to be compatible with the organopolysiloxane, the emulsion stability is remarkably deteriorated, and the initial foam breaking property is also deteriorated. Animal or vegetable oils, fatty acid esters,
Fatty acids and the like may be used.
A combination of more than one species can also be used.

Animal and vegetable oils include, for example, rapeseed oil, soybean oil, bran oil, castor oil, palm oil, tallow, lard, etc., fatty acid esters include tallow fatty acid methyl and methyl oleate, and fatty acids include olein. Acids and isostearic acid can be used.

The amount of the organic solvent or the like is 100
10 to 60 parts by weight, preferably 15 parts by weight,
４０40 parts by weight. If the amount is less than 10 parts by weight, the initial foaming property and the emulsion stability are deteriorated, and if it is more than 60 parts by weight, the initial foaming property and the sustainability of the foam are remarkably deteriorated.

The antifoaming composition of the present invention may contain a stabilizer such as a preservative, a fungicide or a rust inhibitor, if necessary.

The method for producing the antifoaming composition of the present invention includes a method in which an organopolysiloxane composition and an organic solvent are stirred and mixed, an emulsifier and water are added, and the mixture is stirred and mixed to form an emulsion. After stirring and mixing a siloxane composition, an organic solvent and the like and an emulsifier, a method of adding water and stirring and mixing to form an emulsion, and a method of stirring and mixing all the components at once to form an emulsion, and the like. It may be a method. In addition, it is preferable to add a stabilizer such as a preservative, a fungicide, or a rust inhibitor, which is added as needed, simultaneously with the addition of water.

The temperature for stirring and mixing may be adjusted to a temperature that facilitates stirring and mixing according to the viscosity of the organopolysiloxane composition to be used, but is usually preferably 20 to 70 ° C. The stirring and mixing time is not particularly limited as long as the compound can be uniformly mixed, and is usually 10 minutes to 8 hours.

As the stirring and mixing equipment, a blade type stirrer, a dissolver, a homomixer, a ball mill, a sand mill, an ultrasonic disperser, a kneader, a line mixer and the like can be usually used, and two or more of these equipments are used in combination. You can also.

The antifoaming composition of the present invention is subjected to a pulp manufacturing process,
When defoaming in the fiber production / processing step and wastewater treatment step, the composition is directly added to the step part where foaming is to be prevented / suppressed, or the part immediately before the part or the step after the water is fed Add to portions.

For example, specific addition sites in the pulp manufacturing process include a butt portion of a pulp washing, bleaching and concentration device,
Filtrate tanks, tranpo sections, screen devices, etc. In the fiber manufacturing and processing processes, dissolving, defoaming, filtering, washing, spinning, gluing, refining, bleaching, dyeing, printing, finishing and influx of finishing equipment And so on. In the wastewater treatment process, the aeration tank, the inflow portion of the sedimentation tank, an inflow channel, an outflow channel with a head, and the like are used.

The method of adding the defoaming agent composition may be any of continuous addition, intermittent addition, or a method in which a foam measuring machine and an antifoaming agent adding device are linked, and either one-point addition or multi-point addition May be. Upon addition, the mixture may be diluted with a suitable solvent or water or the like, and may be used in combination with another type of antifoaming agent.

[0032]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Hereinafter, "parts" are expressed on a weight basis.

Example 1 30.0 parts of an organopolysiloxane composition [manufactured by Tore Dow Corning Silicone Co., Ltd., trade name SC-5570, viscosity (25 ° C.) 2000 mPa · s], an organic solvent [Idemitsu Kosan Co., Ltd.] 15.0 parts, organic solvent [manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Solvent LA25, kinematic viscosity (40 ° C.) 1.0 cSt] 15.0 parts of sorbitan triolate and 15.0 parts of polyoxyethylene (20 mol) sorbitan triolate as emulsifiers were added to 15.0 parts, and the mixture was stirred and mixed at 30 to 40 ° C. for 20 minutes using a homomixer. 10.0 parts was added and further stirred and mixed for 30 minutes to prepare a W / O emulsion type antifoaming agent of the present invention.

Example 2 60.0 parts of an organopolysiloxane composition [manufactured by Tore Dow Corning Silicone Co., Ltd., trade name SC-5570, viscosity (25 ° C.) 2000 mPa · s], an organic solvent [Sanko Chemical Industry Co., Ltd. ) Made, trade name liquid paraffin 40-
S, kinematic viscosity (40 ° C.) 4.4 cSt] 20.0 parts by emulsifier [trade name FZ2171 manufactured by Nippon Unicar Co., Ltd.] 1
Add 0.0 part and add 3 parts at 40-50 ° C using a blade type stirrer.
After stirring and mixing for 0 minutes, 10.0 parts of tap water was added, and the mixture was further stirred and mixed for 60 minutes to prepare a W / O emulsion type antifoaming agent of the present invention.

Example 3 Organopolysiloxane [SH-200 oil (50c, manufactured by Tore Dow Corning Silicone Co., Ltd.)
St)] 93.0 parts, finely divided silica (Degussa)
AG, trade name SIPERNAT D10) (7.0 parts) was heated with stirring at 180 ° C. for 4 hours to prepare an organosiloxane composition. The viscosity (25 ° C.) of this organopolysiloxane composition was 200 mPa · s. 20.0 parts of the above organopolysiloxane composition were used as an organic solvent as an organic solvent [manufactured by Nippon Oil Co., Ltd., trade name AF Solvent 4, kinematic viscosity (40 ° C.) 2.4 cSt] 30.0 parts and oleic acid 5.0 parts 5.0 parts of rapeseed oil was added, and an emulsifier [KF945A manufactured by Shin-Etsu Silicone Co., Ltd.] 1
After adding 0.0 parts and 5.0 parts of sorbitan monooleate, and adding 5.0 parts of tap water, 3 parts were added using a homomixer.
The W / O emulsion type antifoaming agent of the present invention was prepared by stirring and mixing at 0 to 40 ° C for 60 minutes.

Example 4 50.0 parts of an organopolysiloxane composition [manufactured by Dow Corning Asia Co., Ltd., trade name: FS Anti-Home DB-100, viscosity (25 ° C.) 2500 mPa · s], and [Tore Dow Corning Silicone ( Co., Ltd., trade name BY-28-503, viscosity (25 ° C.) 3000 mPa
2s), and 15.0 parts of tallow fatty acid methyl ester, and 2.0 parts of an emulsifier (trade name: KF945A, manufactured by Shin-Etsu Silicone Co., Ltd.) at 30 to 40 ° C using a homomixer. After stirring and mixing for 20 minutes, 5.0 parts of tap water was added, and the mixture was further stirred and mixed for 30 minutes to prepare a W / O emulsion type antifoaming agent of the present invention.

Example 5 An organopolysiloxane composition [SC-557, trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.]
0, viscosity (25 ° C.) 2000 mPa · s] 15.0 parts and [Toray Dow Corning Silicone Co., Ltd .;
Trade name BY-28-503, viscosity (25 ° C) 3000m
Pa · s] of 15.0 parts, and then 15.0 parts of rapeseed oil.
The mixture was stirred and mixed at 30 to 40 ° C. for 20 minutes using a homomixer, and then used as an emulsifier [Shin-Etsu Silicone Co., Ltd.]
KF945A], 10.0 parts and sorbitan monooleate 5.0 parts were added, followed by 5.0 parts tap water, and further stirred and mixed for 30 minutes to prepare a W / O emulsion type antifoaming agent of the present invention. did.

Example 6 Organopolysiloxane [SH-200 oil (trade name: 60, manufactured by Toray Dow Corning Silicone Co., Ltd.)
000 cSt)] 93.0 parts, finely divided silica (Degu)
manufactured by ssa AG, trade name SIPERNAT D10)
7.0 parts was heated under stirring at 180 ° C. for 4 hours to prepare an organopolysiloxane composition. The viscosity (25 ° C.) of this organopolysiloxane composition is 96,000 mPa
-It was s. The above organopolysiloxane composition 5
0.0 parts of an organic solvent [manufactured by Nippon Oil Co., Ltd., trade name AF Solvent 4, kinematic viscosity (40 ° C.) 2.4 cSt] 2
Add 0.0 parts, and add 2 parts at 30-40 ° C using a homomixer.
After stirring and mixing for 0 minutes, 20.0 parts of [Nippon Unicar Co., Ltd. product name, FZ2171] was added as an emulsifier, and then 10.0 parts of tap water was added, followed by stirring and mixing for another 30 minutes, and the W / An O emulsion type defoamer was prepared.

The following antifoaming agents were used as Comparative Examples 1 to 4. The antifoaming agents of Comparative Examples 1 to 3 are O / W emulsion type silicone antifoaming agents, and Comparative Example 4 is a W / O emulsion type amide-containing antifoaming agent.

Comparative Example 1 An organopolysiloxane composition (trade name: SC-5570, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SC-5570, viscosity (25 ° C.) 2000 mPa · s) was added to 25.0 parts of sorbitan triolate 10.0 as an emulsifier. And 10.0 parts of polyoxyethylene (20 mol) sorbitan oleate were added and mixed at 40 to 50 ° C. for 10 minutes using a homomixer. Next, at the same temperature, 55.0 parts of tap water was added and mixed with a homomixer for 30 minutes, and then cooled to 20 ° C. to prepare an O / W emulsion type antifoaming agent.

Comparative Example 2 25.0 parts of an organopolysiloxane composition [manufactured by Tore Dow Corning Silicone Co., Ltd., trade name SC-5570, viscosity (25 ° C.) 2,000 mPa · s] was used in an amount of 25.0 parts and sorbitan triolate 7.5 as an emulsifier. And 7.5 parts of polyoxyethylene (20 mol) sorbitan triolate and 5.0 parts of a silicone-based emulsifier (trade name L-7001, manufactured by Nippon Unicar Co., Ltd.) and a homomixer at 40 to 50 ° C. Mix for 10 minutes. Next, at the same temperature, 55.0 parts of tap water was added and mixed with a homomixer for 30 minutes.
By cooling to 0 ° C., an O / W emulsion type antifoaming agent was prepared.

Comparative Example 3 30.0 parts of an organopolysiloxane composition (manufactured by Dow Corning Asia Co., Ltd., trade name: FS Anti-Home DB-100, viscosity (25 ° C.) 2500 mPa · s) were mixed with sorbitan triolate 1 as an emulsifier. 0.5 part and 7.5 parts of polyoxyethylene (16 mol) oleyl ether were added and mixed at 40 to 50 ° C. for 10 minutes using a homomixer. Next, at the same temperature, 59.5 parts of tap water was added and mixed with a homomixer for 30 minutes, and then cooled to 20 ° C. to prepare an O / W emulsion type antifoaming agent.

Comparative Example 4 In 50.0 parts of a paraffinic mineral oil (22 cSt, 40 ° C.), 3.0 parts of hydrophobic silica (Nip Seal SS-10, manufactured by Nippon Silica Co., Ltd.) and sorbitan triolate 4.0 as an emulsifier. 0 parts and sorbitan monooleate 2.0
Was added and mixed at room temperature. To this mixture was added 17.0 parts of paraffinic mineral oil (22 cSt, 40 ° C.), 4.0 parts of ethylenebisstearylamide, and then 13 parts.
What was heated and melt | dissolved to 5 degreeC was dripped and mixed under stirring. Next, 20.0 parts of tap water was added to the mixture, the temperature was adjusted to 25 to 35 ° C, and the mixture was mixed for 30 minutes. Finally, the mixture was passed through a high-pressure piston-type emulsifier to prepare a W / O emulsion-type amide-containing antifoaming agent.

Example 7 The antifoaming composition of Example 4 was added to a kraft pulp manufacturing apparatus having a triple vacuum cleaner. The addition step was the No. 1 washing machine vat and the No. 2 washing machine filtrate tank, and was continuously added using a metering pump. Stable operation was possible even with the addition of 100 ppm to the pulp, and the generation of pitch-like aggregates generated in the bleaching step was significantly reduced.

Comparative Example 5 In Example 7, instead of the defoamer composition of Example 4,
The defoamer of Comparative Example 4 was added. In the case of the antifoaming agent of Comparative Example 4, the stable operation can be performed by adding 1000 ppm, but a remarkably large amount of pitch-like aggregates was generated in the bleaching step as compared with Example 6.

Example 8 In the refining and bleaching step of a woven fabric using a jet dyeing machine, the defoamer composition of Example 2 was added intermittently. The addition amount was 40 ppm with respect to the bath, and stable operation was possible.

Comparative Example 6 In Example 8, instead of the defoamer composition of Example 2,
The defoamer of Comparative Example 1 was added. In the case of the antifoaming agent of Comparative Example 1, even when 40 ppm was added, the refining bleaching solution overflowed from the bath, and stable operation was not possible. For stable operation,
The antifoaming agent of Comparative Example 1 required 200 ppm.

Example 9 The defoamer composition of Example 3 was added to an activated sludge treatment apparatus for treating kraft pulp, papermaking, and deinking wastewater.
The addition sites were the inlet of the aeration tank and the outlet of the river, and continuous addition was performed using a metering pump. Addition amount is 2p for wastewater
Stable operation at pm.

Comparative Example 7 In Example 9, the antifoaming composition of Example 3 was replaced with
The defoamer of Comparative Example 2 was added. In order to operate stably with the defoamer of Comparative Example 2, 50 ppm was required.

The performances of the defoamer compositions of Examples 1 to 6 and the defoamers of Comparative Examples 1 to 4 were evaluated by the following methods.

Defoaming performance test Foaming test water, that is, a refining process solution, was added to a glass foam tube.
Pulp production process black liquor, papermaking wastewater treatment process solution 500m each
and heated and maintained at a predetermined temperature, and a test water was flowed at a flow rate of 2000 ml /
Then, the liquid was dropped from the upper part of the foaming tube to the test water surface and circulated, whereby the test water was foamed. When the foam height reaches 10 cm due to the circulation of the test liquid, a predetermined amount of an antifoaming agent (Examples 1 to 6 and Comparative Examples 1 to 4) is added, and the foam height reaches 10 cm or progresses. The changing foam height (cm) was measured with elapsed time until the time reached 90 seconds, and the results are shown in Tables 1-3. The blank portion in the table indicates that the bubble height became 10 cm or more (overflow).

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

Emulsion stability test In a 200 ml glass bottle, an antifoaming agent (Examples 1 to 6, Comparative Example 1)
To 4), and allowed to stand at each temperature of 5 ° C., 25 ° C., and 40 ° C. for one month, and visually observed the separation stability.
It was shown to. The criteria are as follows. ：: no difference compared to before stability test △: inferior to before stability test (slight separation) ×: remarkably inferior to before stability test (large separation and change in product appearance) Is recognized.)

Mechanical Stability Test An antifoaming agent (Examples 1 to 6 and Comparative Examples 1 to 4) was circulated for 5 hours using a gear pump at a flow rate of 2000 ml / min, and the mechanical stability was visually observed. Are shown in Table 4. The criteria are as follows. ：: No difference compared to before the stability test. 劣: Inferior to before the stability test (a slight change in the appearance of the product is observed). X: Remarkably inferior to that before the stability test. Product appearance change is observed.)

Measurement of pitch ratio of antifoaming agent itself 500 g of pulp production process black liquor was placed in a 1000 ml stainless steel beaker and heated and maintained at 85 ° C., and 5.0 g of an antifoaming agent (Examples 1 to 6, Comparative Examples 1 to 4) ) And uniformly stirred for 30 minutes at 85 ° C. Subsequently, the mixture was filtered through a box-shaped bent 100-mesh stainless steel wire mesh of known weight, and washed with 1000 ml of 80 ° C hot water. The filtered wire mesh was air-dried all day and night, the residue on the 100 mesh wire mesh was weighed, and the pitch ratio was calculated by the following formula. The results are shown in Table 4. Pitch ratio (%) = [residue (g) on 100 mesh wire net] × 100 / [amount of added antifoaming agent (5.0 g)]

[0058]

[Table 4]

[0059]

EFFECTS OF THE INVENTION The W / O emulsion type antifoaming composition of the present invention has better emulsion stability and initial foam breaking property than conventional O / W silicone emulsion type antifoaming agents and oil type antifoaming agents. It has extremely excellent defoaming performance with sustained foaming, and has particularly excellent defoaming performance even under severe conditions such as high temperature, high alkali and high shearing force. Further, since it has little occurrence of pitch-like aggregates and does not contain a dioxin precursor, it is suitable as an antifoaming agent for pulp manufacturing processes, fiber manufacturing / processing processes, and wastewater treatment.

In addition, since only a very small amount of addition is required, there is an advantage that a small amount of inventory is sufficient, the number of storage places and empty containers is reduced, and large-scale equipment for unloading work and transfer is not required. It is.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09K 3/00 C09K 3/00 Z D01D 1/10 D01D 1/10 D21C 3/28 D21C 3/28 // C11D 3/37 C11D 3/37 (58) Field surveyed (Int.Cl. ⁷ , DB name) B01D 19/04

Claims (2)

(57) [Claims] 1. A. First Embodiment The viscosity at 25 ° C. of the organopolysiloxane and the finely divided silica is 50 to 200,0.
B. 10 to 88 parts by weight of one or more organopolysiloxane compositions having a pressure of 00 mPa · s. Emulsifier 1 to 50 parts by weight C.I. 1 to 50 parts by weight of water One or more organic solvents having a kinematic viscosity at 40 ° C. of 0.5 to 11 cSt and / or an animal or vegetable oil or / and a fatty acid ester selected from tallow fatty acid methyl and methyl oleate or / and oleic acid and isostearic acid Fatty acids 10-6 selected from
A W / O emulsion type antifoaming composition comprising 0 parts by weight. 2. A defoaming method wherein the W / O emulsion type antifoaming composition according to claim 1 is added and used in a pulp production step, a fiber production / processing step or a wastewater treatment step.