JP2002191906A - Higher alcohol type emulsion defoaming agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a higher alcohol type emulsion defoaming agent composition having more excellent initial foam breaking properties and foam suppression lasting properties even at a water temperature of a high temperature region exceeding 40 deg.C. SOLUTION: The higher alcohol type emulsion defoaming agent composition contains 100 pts.wt. of (A) higher alcohols with a melting point of 40-100 deg.C, 10-50 pts.wt. of (B) fatty acid esters with a melting point of 4-100 deg.C and 5-50 pts.wt. of (C) a surfactant comprising an alkylene/polyglycol copolymer of which both terminals are blocked by fatty acid ester and/or alcohol and having defoaming effect.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to process water in various manufacturing industries such as the pulp and paper industry, the petrochemical industry, the textile industry, and the paint industry, and foaming in the water system of wastewater treatment processes such as factory wastewater, municipal sewage and night soil treatment plants. Antifoaming agent to suppress
And a method for manufacturing the same.

[0002]

2. Description of the Related Art An oil-in-water emulsion defoaming agent containing a higher alcohol as a main component is used as an industrial defoaming agent [JP-A-48-
No. 62683] is widely used in the paper pulp industry, coating industry, textile industry, wastewater treatment, etc. because of its relatively low price and high defoaming effect. For example, in the paper and pulp industry, it has been recognized that the oil-in-water emulsion defoaming agent has an excellent defoaming agent effect and also has little influence on the size, and its use has been rapidly expanded. But,
Recently, recycling of process water in the pulp and paper industry has progressed,
Conventional water-in-water emulsion defoaming agents became more vigorous due to the fact that the process water temperature was 40°C or higher, the number of neutral papermaking increased, and the amount of chemicals used increased due to the higher quality of paper. Then I'm not always satisfied. As a result, conventionally, the oil-in-water emulsion defoaming agent containing a higher alcohol as a main component was relatively excellent in the initial defoaming property, but in recent years, not only the initial defoaming property but also the improvement of the foam suppressing durability is required. It has been.

Therefore, as a method for improving the defoaming effect,
A method in which a higher alcohol having a large number of carbon atoms, a fatty acid ester and a wax are used in combination [JP-A 1-2
No. 10005, JP-A-8-257305],
A method of combining a higher alcohol, a higher fatty acid ester, a higher fatty acid polyglyceride, and a higher fatty acid polyalkylene glycol [JP-A-8-501834],
A method of using a combination of a higher alcohol, a higher fatty acid ester, a ketone, and a wax having a melting point of a specific temperature or higher [JP-A 8-510160], and adding a polyglycol having an alkyl group at the end to obtain a defoaming effect. A method of improving [JP-A-8-113891] and the like have been proposed. However, a higher alcohol emulsion defoaming agent having both satisfactory initial foam breaking property and satisfactory foam suppressing property has not yet been obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a higher alcohol-based emulsion defoaming agent composition having excellent initial defoaming property and long-lasting depressurization property even at a water temperature in a high temperature range exceeding 40° C. To do.

[0005]

Means for Solving the Problems As a result of intensive studies on the defoaming effect and emulsion stability of a higher alcohol emulsion defoamer in a high temperature range, the present inventors have found that a specific alkylene polyglycol copolymer Ester and/or end-capped with fatty acid and/or alcohol
Or, by adding an ether type surfactant to a higher alcohol emulsion defoaming agent, it was found that an emulsion defoaming agent having a defoaming effect with improved initial defoaming property and foam suppression durability can be obtained. The present invention has been completed.

That is, the present invention (A) has a melting point of 40 to
100 parts by weight of higher alcohols at 100° C., (B) 10 to 50 parts by weight of fatty acid esters having a melting point of 40 to 100° C.,
(C) A higher alcohol emulsion defoamer composition comprising 5 to 50 parts by weight of a surfactant represented by the general formula (1).

[0007]

[Chemical 2]

Here, X, Y: —COO—, —O— R ¹ , R ² : a linear or branched alkyl group having 8 to 30 carbon atoms a: an integer of 5 to 30 b: an integer of 5 to 30 And a≧b

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

In the higher alcohol emulsion defoamer composition of the present invention, the component (A) is a higher alcohol, has a melting point of 40 to 100° C., preferably 45 to 90° C., and is of a saturated type or an unsaturated type. Any of them may be a mixture, either a linear type or a branched type, or a mixture,
Furthermore, either a natural alcohol or a synthetic alcohol, or a mixture thereof may be used. When the melting point of the higher alcohol is less than 40°C, the defoaming effect may not be sufficiently exhibited when the liquid temperature of the system to which it is applied is higher than 40°C. It is difficult to obtain and not practical.

Examples of higher alcohols having a melting point of 40 to 100° C. include cetyl alcohol, stearyl alcohol, eicosanol, docosanol (behenyl alcohol), tetracosanol, hexaconol, octaconol, myricyl alcohol, and melting points synthesized by the oxo method. Examples include higher alcohols having a temperature of 40 to 100° C. and higher alcohols having a melting point of 40 to 100° C. synthesized by the Ziegler method. Further, the distillation residue of synthetic alcohol may be used.

The component (B) of the present invention is a fatty acid ester and has a melting point of 40 to 100°C, preferably 45 to 90°C.
Is. The fatty acid or alcohol constituting the fatty acid ester may be either saturated or unsaturated, linear or branched, natural or synthetic, or a mixture thereof. Fatty acid esters having a melting point of less than 40° C. are not preferable because they may not exhibit a sufficient defoaming effect when the liquid temperature of the system to which they are applied is high such that they exceed 40° C. Further, a fatty acid ester having a melting point of higher than 100° C. is not preferable because the defoaming effect is not improved so much and the emulsion stability is poor.

Examples of fatty acid esters having a melting point of 40 to 100° C. are stearyl stearate, behenyl behenate, ethylene glycol distearate, diethylene glycol distearate, triethylene glycol distearate, monoglyceride stearate, diglyceride stearate, pentaglyceride distearate. Erythritol, pentaerythritol tetrastearate, sorbitan monostearate, sorbitan distearate and the like can be mentioned.

The blending amount of the component (B) is 100 parts of the component (A).
10 to 50 parts by weight, preferably 20 to 40 parts by weight
Parts by weight. If it is less than 10 parts by weight, the defoaming effect is not sufficiently improved, and if it is more than 50 parts by weight, the defoaming effect is not greatly improved for the blending amount, which may be economically disadvantageous.

The component (C) of the present invention is a surfactant represented by the general formula (1), which is a defoaming product in which both ends of an alkylene polyglycol copolymer are blocked with a fatty acid ester and/or an ether with an alcohol. It is an ester-ester type, ester-ether type, or ether-ether type surfactant having an effect, and contains one or more of them.

[0016]

[Chemical 3]

In the general formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 8 to 30 carbon atoms, preferably a linear alkyl group having 10 to 22 carbon atoms, More preferably, it is a linear alkyl group having 12 to 18 carbon atoms. If the alkyl group has less than 8 carbon atoms, the defoaming effect may not be obtained in some cases, and if the carbon number exceeds 30, the effect may be improved but the industrial availability may be difficult.

X and Y each independently represent an ester bond and an ether bond. a represents the number of moles of ethylene oxide added, and is an integer of 5 to 30, and when a is less than 5, sufficient improvement of the defoaming effect may not be observed,
If a exceeds 30, the effect may not be improved in proportion to the increase in the number of moles of ethylene oxide added. b represents the number of moles of propylene oxide added, 5
It is an integer of -30, and when b is less than 5, a sufficient improvement of the defoaming effect may not be observed, and when b exceeds 30, the improvement of the effect which is commensurate with the increase in the number of moles of propylene oxide added is obtained. You may not be able to. a is equal to b,
If it is larger than b, and a is larger than b, sufficient improvement of the defoaming effect may not be seen.

The alkylene polyglycol copolymer of ethylene oxide and propylene oxide may be either random polymerization or block polymerization.

The surfactant as the component (C) can be produced by a general method, for example, an ether in which both ends of an ethylene oxide and propylene oxide copolymer are blocked with a higher alcohol and a higher fatty acid. In the case of an ester-type surfactant, ethylene oxide and propylene oxide are added in a predetermined amount to higher alcohols using sodium hydroxide as a catalyst, and further esterified with higher fatty acids to obtain the desired product. Further, in the case of an ester-ester type surfactant in which both ends are blocked with a higher fatty acid, a copolymer of a predetermined ethylene oxide and propylene oxide is prepared and reacted with a higher fatty acid or its higher fatty acid chloride to obtain the desired product. There is no particular limitation.

The amount of component (C) used in the present invention is 5 to 50 parts by weight, preferably 10 parts by weight, per 100 parts by weight of component (A).
-25 parts by weight. If it is less than 5 parts by weight, the improvement of the defoaming effect may not be sufficient, and if it is more than 50 parts by weight, the improvement of the defoaming effect may not be great relative to the blending amount, which may be economically disadvantageous. ..

The higher alcohol emulsion defoaming agent of the present invention is characterized by containing components (A), (B) and (C). In addition, a polysaccharide thickener and a cellulose thickener are used for preventing the separation of the emulsion. Thickener, emulsifier for emulsion preparation,
It contains water.

Examples of the thickener used in the higher alcohol emulsion defoaming agent of the present invention include welan gum, xanthan gum, guar gum and rhamsan gum as polysaccharide thickeners, and hydroxymethyl cellulose and hydroxy as cellulose thickeners. There are ethyl cellulose, hydroxymethyl propyl cellulose and the like, and one or more of them are used. The blending amount is 0.01 to 0.5 part by weight with respect to the higher alcohol emulsion defoamer.

The surfactant used when producing the higher alcohol emulsion defoamer composition of the present invention is
Although not particularly limited, it is generally selected from anionic surfactants and nonionic surfactants. Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium oleyl sulfate, water-soluble fatty acid salts such as sodium laurate and sodium oleate,
There are water-soluble dialkylsulfosuccinates such as sodium dioctylsulfosuccinate, water-soluble ligninsulfonates such as sodium ligninsulfonate, alkylnaphthalenesulfonates, α-olefinsulfonates, and alkylbenzenesulfonates.

Examples of the nonionic surfactant include sorbitan monooleate and sorbitan dioleate sorbitan fatty acid esters, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan distearate polyoxyethylene sorbitan fatty acid esters, and the like. Polyoxyalkylene fatty acid esters such as polyoxyethylene oleate and polyoxyethylene polyoxypropylene oleate, polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene oleyl ether, polyoxyethylene nonylphenol Ether) and polyoxyalkylene alkylphenol ethers such as polyoxyethylene octylphenol ether.

The compounding amount of the surfactant varies depending on the components in the emulsion, the kind of the surfactant and the like and cannot be uniformly determined, but it is generally 0.1 to 5 wt% with respect to the emulsion to be produced. ..

In the production of the higher alcohol emulsion defoaming agent of the present invention, the component (C) is blended with the component (A) and the component (B) which are heated and melted in an oil phase component, and an oil-in-water emulsion. There is, for example, a method of blending with water to be used when preparing, but the embodiment of the method for producing a preferable antifoaming agent is not particularly limited,
A temperature that does not exceed 110° C., which is higher than the melting point of either component (A) or component (B), which is higher than that of component (A), component (B), and component (C), by uniformly stirring and mixing. And vigorously agitate with water and a surfactant heated to a temperature not exceeding 100° C., which is higher than the melting point of either component (A) or component (B), whichever is higher, and exceeds 100° C. A method for producing a higher alcohol emulsion defoamer composition, which comprises preparing an emulsion at a non-existing temperature and then cooling it to room temperature. It is desirable to preheat the water used in the production of the emulsion, and its temperature varies depending on the temperature of the oil phase mixture and the mixing ratio of water,
It is usually 60 to 80°C.

The amount of water used for preparing the emulsion varies depending on the compounds contained in the oil phase mixture and is not uniformly determined, but usually, oil phase mixture:water=1:1 to 1:1:
5 (weight ratio). The emulsion may be prepared by adding the oil phase mixture while vigorously stirring water.

In producing the emulsion, the particle size of the emulsion is observed using a particle size distribution meter, and the stirring is continued at a predetermined emulsification temperature until the emulsion particle size reaches 0.5 to 15 μm, and then the stirring is further continued. While it is better to cool to room temperature.

The stirring device used for preparing the emulsion is not particularly limited, but for example, a propeller type stirrer, a dissolver, a homomixer, a line mixer,
There are a kneader, a high-speed rotary high-shear stirrer, a colloid mill, an ultrasonic emulsification disperser and the like.

Other optional components may be added within a range that does not impair the defoaming effect of the present invention. For example, organopolysiloxanes with antifoaming effect, other polyglycol antifoaming agents, other water-soluble polysaccharides, polyacrylic acid (or its salt), water-soluble synthetic polymer compounds such as polyacrylamide, permeability Nonionic surfactants or anionic surfactants may be added for the purpose of improving the composition, or a bactericide for preventing spoilage of the emulsion, other mineral oils may be added, but the present invention limits the combined use of these additives. is not.

The defoaming agent of the present invention is used by directly adding it to the foaming liquid, or by adding it to the step immediately before the location where foaming occurs. Further, the addition method is selected according to the situation and is not particularly limited, but it is generally added by using a pump.

The amount of the defoaming agent of the present invention to be added varies depending on the conditions of the target system and the necessity of defoaming, but generally 1 to 100 ppm is the standard for the foaming liquid.

[0034]

[Carbon number: 16-20, melting point: 45-49°C, manufactured by Condea]

A-2: Behenyl alcohol for industrial use [carbon number: 18-24, melting point: 64-71°C, manufactured by Condea] A-3:1-docosanol [carbon number: 22, melting point: 72°C, manufactured by Tokyo Kasei Co., Ltd.] Reagent] A-4: (Comparative Example) Lauryl alcohol [melting point: 23-24°C, manufactured by NOF Corporation] [B component] B-1: pentaerythritol distearate [melting point: 54°C, NOF Corporation] B-2: behenyl behenate [melting point: 73° C., NOF Corporation] B-3: tristearic acid glyceride [melting point: 74-78° C., NOF Corporation] B-4: curing Beef tallow [melting point: 43-47°C, manufactured by NOF Corporation] B-5: (comparative example) methyl stearate [melting point: 31-35°C, manufactured by NOF Corporation] [C component] C-1: Octyl polyoxyethylene (5 mol) polyoxypropylene (5 mol) octyl acid ester C-2: oleyl polyoxyethylene (15 mol) polyoxypropylene (10 mol) stearic acid ester C-3: polyoxyethylene (30 mol ) Oxypropylene (15 mol) dibehenic acid ester C-4: Polyoxyethylene (10 mol) Polyoxypropylene (10 mol) Copolymer both-terminal dodecyl ether [Others] D-1: Sorbitan monooleate [NOF CORPORATION] (stock)
"Nonion OP-80R" (trade name)] D-2: Polyoxyethylene sorbitan monooleate [Nonion OT-221" (trade name) manufactured by NOF CORPORATION] D-3: Ethylene glycol [ Wako Pure Chemical Industries, Ltd., reagent] D-4: Polyethylene oxide (10 mol addition) dihexanoic acid ester D-5: Zansan gum (Sansei Co., Ltd.) (Preparation of higher alcohol emulsion defoamer-1) 2
Water: 710 g, xanthan gum: 1 g were put in a 000 mL steres container, and a stirrer with three screw blades was used.
The mixture was stirred to form a uniform aqueous solution and heated to 80°C (water (1)).
On the other hand, 1000 mL of stainless steel beaker has 1 carbon
6-20 Ziegler synthetic alcohol (A-1): 2
00 g, pentaerythritol distearate (B-
1): 50 g, octyl polyoxyethylene (5 mol)
Polyoxypropylene (3 mol) octylate (C-1): 20 g, sorbitan monooleate (D-1): 10 g and polyoxyethylene sorbitan oleate (D-2): 10 g were added,
While stirring, the mixture was heated to 80° C., mixed and melted to prepare a mixture (1). Next, water (1) heated to 80° C. was added to 5,000
Add to warmed mixture (1) while stirring at 8 rpm,
Stirring was continued for 2 hours while maintaining 0°C. Then, heating was stopped, and stirring and cooling were continued until the temperature reached 30°C.
During this period, the emulsion particle size was measured with a laser diffraction type particle size distribution analyzer LA-500 (manufactured by Horiba Ltd.), and the particle size was 5 μm.
Then, the defoaming agent-1 was prepared.

Defoaming agents-2 to 10 and defoaming agents-12 to 14 having the compositions shown in Table 1 were prepared in the same manner.

[0036]

[Table 1]

(Higher alcohol emulsion defoamer-
Preparation of 11) Preparation of defoaming agent-1 except that oleyl polyoxyethylene (10 mol) polyoxypropylene (10 mol) stearic acid ester was mixed with water (1) in the method for preparing defoaming agent-1. Antifoam-11 was prepared in a similar manner without changing the method. (Defoaming performance evaluation method) Neutral neutral coated base paper making process White water (pH: 7.5, liquid temperature 45°C) is heated to 30°C and 45°C, and the defoaming test device shown in Fig. 1 is obtained. 1000mL into a cylindrical container made of acrylic resin, and add 4.5% of white water with a circulation pump.
It was circulated at a flow rate of L/min to foam. The foam height due to foaming was determined as the foam height by measuring the height of the liquid surface due to foaming with reference to the height of the liquid surface when 1000 ml of white water was added. In the defoaming test, heated white water is circulated so that the foam height is 1
When it reached 00 mm, 20 mg (20 ppm) of the defoaming agent was added from the top of the acrylic resin cylindrical container, and the foam height was measured and recorded every 20 seconds immediately after the addition of the defoaming agent. The circulation was performed for 120 seconds. The results are shown in Table 2. The defoaming agent of the present invention greatly improved the initial foam breaking property and the sustained foam suppressing property.

[0038]

[Table 2]

(Separation Inhibition Test of Higher Alcohol Emulsion Defoaming Agent) Each of the prepared higher alcohol emulsion defoaming agents was placed in a graduated 1,000 ml graduated cylinder, covered and placed in a constant temperature bath at 40° C. I let it stand. Two weeks and one month after standing, the volume of the lower clarification part due to the sedimentation of the emulsion defoaming agent in the 1,000 ml graduated cylinder was measured, and the volume was evaluated based on the ratio to the total amount. The smaller this ratio is, the more preferable. The results are shown in Table 3. (Viscosity stability test of higher alcohol emulsion defoamer) Each of the prepared higher alcohol emulsion defoamers was placed in a 500 ml wide-mouth bottle, covered with a lid, and allowed to stand in a constant temperature bath at 40°C immediately after preparation. The viscosity was measured after 1 month of standing. To measure the viscosity, put the rotor of B-type rotational viscometer in a wide-mouthed bottle and rotate the rotor at 25°C and 20 rpm.
The viscosity was calculated by measuring 1 minute after the start of rotation. Those that do not change into a creamy form with a small change in viscosity are preferred. Further, the higher alcohol-based emulsion defoaming agent was taken, and the presence or absence of gel or aggregate was visually observed. A gel-like material or a material free from aggregates is preferable. The results are shown in Table 3.

[0040]

[Table 3]

[0041]

The higher alcohol emulsion defoaming agent of the present invention is excellent in initial defoaming property and sustained foam suppressing property, and has a high defoaming effect in a smaller amount than the conventional higher alcohol emulsion defoaming agent. Emulsion viscosity change and separation is small, product stability is greatly improved, paper pulp industry,
It greatly contributes to the suppression of foaming and defoaming in the water system of process water in various manufacturing industries such as petrochemical industry, textile industry, paint industry, factory wastewater, wastewater treatment process such as municipal sewage and night soil treatment plant.

[Brief description of drawings]

FIG. 1 is a schematic view of a defoaming test apparatus.

[Explanation of symbols]

1 Circulation pump 2 Liquid supply pipe 3 Test tube 4 Defoamer 5 Foaming liquid

Claims (1)

[Claims] 1. (A) 100 parts by weight of a higher alcohol having a melting point of 40 to 100° C., (B) 10 to 50 parts by weight of a fatty acid ester having a melting point of 40 to 100° C., and (C) a general formula (1).
A higher alcohol emulsion defoamer composition comprising 5 to 50 parts by weight of a surfactant represented by: [Chemical 1] Here, X, Y: -COO -, - O- R 1, R 2: linear or branched alkyl group having 8 to 30 carbon atoms a: 5 to 30 integer, b: 5 to 30 integer and, a≧b