WO2006033450A1

WO2006033450A1 - Silica fouling inhibitor and method of fouling prevention

Info

Publication number: WO2006033450A1
Application number: PCT/JP2005/017904
Authority: WO
Inventors: Tomoo Kato; Ikuko Nishida
Original assignee: Kurita Water Industries Ltd.
Priority date: 2004-09-24
Filing date: 2005-09-20
Publication date: 2006-03-30
Also published as: JP4654644B2; JP2006088036A

Abstract

A silica fouling inhibitor which comprises either a copolymer having (meth)acrylic acid units and monomer units having a sulfo group, the proportion of the monomer units having a sulfo group exceeding 10 mol%, or a copolymer having carboxy and sulfo groups, the sulfo group/carboxy group molar ratio being 0.15-2.0; and a method of preventing silica fouling, characterized by adding either of the copolymers to circulating water. Use of the silica fouling inhibitor is effective in preventing silica fouling in a cooling water system, etc.

Description

TECHNICAL FIELD Field of the Invention

The present invention relates to an anti-adhesive agent for silica-based soil and an anti-sticking removal. In more detail, the present invention relates to an anti-slipping agent and anti-sticking agent for scouring-type soils that can effectively stop the adhesion of silica-based soils generated in cooling water systems, boiler water systems, B-hardness systems, etc. Regarding the method. Background

Conventionally, as a silica-based scale inhibitor, low molecular weight polymers having a canoleboxyl group such as attalinoleic acid and maleic acid, low molecular weight polyacrylamide, fosphonic acid, and polylin swelling are known. For example, as a silica-based scale inhibitor for water containing high silica, a silica-based scale containing a poly (meth) acrylamide having a molecular weight of 2100 to 10, 0,000, a P-type Jt agent has been used (Patent Document 1). ). Further, as a scale inhibitor which exerts an excellent effect against the biasing adhesion prevention Siri force based scale and calcium-based Sukenore, a N- vinyl formamidine de single is Ν Bulle § Seto amide units 5 0 mole ^_0/0 or more (Patent Document 2) _{0 In} addition, as a scale inhibitor that is particularly excellent in the P-direction stopping effect of siri-force scales, (poly) An anti-scaling agent containing a product of an alkylene polyamine or a derivative thereof #: and an ethylenically unsaturated compound is obtained (Patent Document 3). These conventional polymers for preventing phosphonic scale were intended for high-temperature scales that adhere mainly to heat, such as calcium carbonate, phosphate, and phosphorus. In addition, the conventional silica-based scale inhibitor also has a magne and n-um content multi-scaling force scaler that adheres to the high temperature part.

In recent years, the silica-based soils on which aluminum is involved have become a problem. Due to the water quality of the water source, the concentration of aluminum derived from? ^^ U used for turbidization of industrial water tends to increase. It was newly found that silica-based soil containing silica and aluminum adheres when water with high aluminum concentration is used. In addition, in S ^ Offi for irrigation water, it was found that if the padding with a key agent was performed as a pretreatment to prevent clogging of the membrane, the scouring system stains would stick to the membrane. Low temperature scouring stains are exposed to heat. Not only does it cause bowing I, but also adheres to non-si® pipes. For example, in a cooling water system, a failure in which a predetermined cooling capacity cannot be obtained due to a decrease in the cooling water flow rate, a failure in which cooling efficiency is reduced due to a scouring force soil adhering to the cooling tower, or a silli force soiling adhering to the cooling tower Causes peeling and clogging in the heat exchanger. The water-soluble polymers that have been shelved in the past against silica-based soils adhering to these low-temperature parts have a certain anti-sticking effect, but they are not at a satisfactory level.

Astronomical literature 1] Japanese Patent Application Laid-Open No. 6 1-1 0 7 9 9 7 (page 1)

[Patent Document 2] Japanese Patent Application Laid-Open No. Hei 10 0-3 2 3 6 96 (2nd page)

[Patent Document 3] Japanese Patent Application Laid-Open No. 11-29 0 8 9 1 (Page 2) Disclosure of Invention

The present invention provides an anti-slipping agent and anti-sticking agent for siri-based soils that can effectively prevent silica-based soils generated in cooling water systems, boiler water systems, etc. It was made for the purpose.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone group, and having a sulfone example. Thread loss ratio of monomer unit is 1. A copolymer having more than mol%, or a copolymer having a carboxyl group and a sulfone ^ ¾, wherein the molar ratio of sulfone ^ / carboxyl group is 0.15 ~

2. It was found that by adding the copolymer of 0 to the water system, the adhesion of siri-type soil in the τΚ system can be effectively prevented. Invented the invention. That is, the present invention

(1) An anti-sticking agent for siri-based soil containing a copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone m¾, and a monomer having a sulfone bond in a self-copolymer An anti-sticking agent for scouring-type soils with a unity yarn destruction ratio exceeding 10 mol%,

(2) The antifouling agent for silica-based soils according to (1), wherein the monomer having a sulfone cocoon is 2-attalinoleamido-2-methylpropanesulfonic acid,

(3) Adhesion of silicic force-based soil containing a copolymer having a carboxyl group and sulfone ^ S, a P-stopping agent, the molar ratio of sulfone ^ SZ carboxyl group being 0.15 to 2.0 This is an anti-fouling system for soil-based dirt (J, (4) A copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone group in circulation, and the yarn loss ratio of the monomer unit having a sulfonic acid group in the ftlf self-copolymer is

Prevention of adhesion of soil-based soils based on the addition of more than 10 mol% of copolymer; ^

(5) The monomer having a sulfonic acid group is 2-acrylamido-2-methylpropane sulfonic acid (4) A method for preventing adhesion of silica-based soil of the texture, and

(6) It is necessary to add a mixture of a copolymer having a carboxyl group and a sulfonic acid group, wherein the molar ratio of the sulfone carboxyl group is 0.15 to 2.0. A method to prevent adhesion of scouring system dirt

It is something to do. Brief Description of Drawings

Fig. 1 is a construction diagram of the model bride and water rejection system used in the male and comparative examples. In the figure, reference numeral 1 is a machine tank, 2 is a thread R pump, 3 is a circulation pit, 4 is a circulation pump, 5 is a tank, 6 is a tower, and 7 is a dredge tube. Best mode for carrying out the invention

The first aspect of the adhesion preventive agent for scouring soils according to the present invention is an adhesion preventing agent for scouring soils containing a copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone. , yarn dark ratio forces of the monomer units having a sulfonic ^ S in 'bad himself copolymer, an adhesion inhibitor of silica stains more than iota 0 mol ^_0/0. If the yarn loss ratio of the monomer unit having a sulfone is 10 mol% or less, the effect of preventing the adhesion of silica-based soils may be reduced in the circulating water system.

Examples of the monomer having a sulfone used in the present invention include vinyl sulfonic acid, linoles norephonic acid, styrene sulfonic acid, 2-atarylamide _ 2-methylpropane sulfonic acid, 2-methacrylamide 1-methylpropane sulfonic acid. 4-methacrylic acid 4-sulfobutyl, aryloxybenzene sulfonic acid, metallinoleoxybenzene sulfonic acid and the like, and salts thereof. Of these, 2-acrylamido-2-methylpropanesulfonic acid can be used particularly for Example 1.

The second type of the adhesion preventive agent for siliceous soils according to the present invention is a silica-based soil adherence preventive agent containing a copolymer having a strong lpoxyl group and a sulfone ^ S, which is a sulfonic acid group / carboxyl group. This is an anti-fouling agent for silica-based soils having a molar ratio of / l group of 0 · 15 to 2.0. Even if the molar ratio of sulfone soot / carboxyl group is less than 0.15 or more than 2.0, the effect of preventing the adhesion of silica-based soils may be reduced in the circulating water system.

Examples of the monomer having a carboxyl group used in the present invention include attalinoleic acid, methacrylic acid, crotonic acid, isocrotonic acid, anglycylic acid, tiglic acid, maleic acid, fumaric / relic acid, itaconic acid, citraconic acid, and mesaconic acid.ビ -vininobenzoic acid, atrono, triacid, etc., their salts, their anhydrides, and the like.

In the present invention, a monomer having a canolepoxyl group and a monomer having a sulfone can be used in one kind each for war insects, or two or more kinds can be used in combination. Among the copolymers obtained by copolymerizing these monomers, the copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid has a great effect of preventing silicic system stains. Particularly suitable for use. '

There is no particular limitation on the molecular weight of the copolymer of the monomer having a canolepoxyl group and the monomer having a sulfone cage used in the present invention, but the weight average molecular weight is from 1, 0 0 to 50, 0 0 0 Preferably, it is 3, 0 ° 0 to 2 0, 0 0 0. If the weight average molecular weight of the copolymer is less than 1,00, the effect of preventing the adhesion of scouring system stains may not be sufficiently exhibited. If the weight average molecular weight of the copolymer exceeds 50, 00, the viscosity of the copolymer at night may increase, and the copolymer may be degraded. The weight average molecular weight of the copolymer can be determined by using gel oxide chromatography as polyethylene oxide as a standard substance.

The method for producing a copolymer of a monomer having a carboxyl group and a monomer having a sulfone used in the present invention is not particularly limited, and examples thereof include soot polymerization and overnight polymerization. Monomers having a carboxyl group, monomers having a sulfone group, and copolymers thereof are water-soluble in many cases. Therefore, it is preferable to use a water pool combination that uses water. it can. A monomer having a carboxyl group, a monomer having a sulfone group, and water are dissolved in water, and the atmosphere is replaced with an inert gas. Peroxo-sodium potassium, hydrogen peroxide, 2,2'-azobis (2-methylpropionamidine), etc. The water-soluble radical polymerization of the copolymer can be obtained by heating with the addition of J. According to the water-soluble liquid polymerization, the weight of the copolymer is determined by selecting the polymerization tank. The molecular weight and molecular weight distribution of the coalesced can be easily controlled, and the water retention time of the obtained copolymer is used as it is as an anti-fouling agent for silica-based soils. Power to use S

In the context of the present invention, a ternary or higher copolymer having another monomer unit can be used as the copolymer having a monomer unit having a carboxyl group and a monomer unit having a sulfone group. 7 When producing a copolymer by intense night polymerization, other monomers to be copolymerized include, for example, methyl acrylate, 2-hydroxyethyl acrylate, acrylonitrile, N-vinyl pyrrolidone, etc. .

In the first embodiment of the method for preventing adhesion of scouring system dirt of the present invention! / Is a copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone group in the circulation R, and a yarn destruction ratio of the monomer unit having a sulfone group in the anionic polymer. Insect copolymers with more than 10 mol%. In the method of the present invention, the monomer having a sulfonic acid group of the copolymer is preferably 2-acrylamido-2-methylpropanesulfonic acid. In the second method # of the method for preventing adhesion of silica-based soil according to the present invention, there is provided a copolymer having a carboxyl group and a sulfonic acid group, which is a sulfonic acid group and a carboxyl group. The molar ratio of 0.15

2. Make a copolymer that is 0.

In the present invention, there is no particular limitation on the location where the copolymer having a carboxyl group and sulfone β is fed into the circulation R, and it is possible to directly feed into the location where the sill-type soil adheres. Yes, or it can be attached to any point before that point. For example, in a cooling water system, it can be connected to any part of the heat ¾ ^ body, circulation 7_k pit, cooling tower piping line, etc., or connected to the circulation system. It is also possible to pre-roll to When applying the present invention, there are no particular restrictions on water quality conditions, boilers, heat exchange conditions, etc., and normal water quality, boiler, heat exchange conditions, etc. can be used. Although the detailed action that can effectively prevent the adhesion of the scouring-type soil by the adhesion-preventing agent and the adhesion-preventing method of the present invention is unclear, the monomer unit having a carboxyl group and the sulfone group are not known. A copolymer having a monomer unit having a sorbent adsorbs on a deposit of silicic force having aluminum as a nucleus, and the deposit is separated into water to prevent adhesion of silica-based soil. Queue

Hereinafter, the present invention will be described in more detail with reference to male examples. However, the present invention is not limited to these examples. In the implementation column and comparison column, consultation was conducted using the five-unit type decree water system shown in Fig. 1. Kawasaki City industrial water (5.5 t) was sampled and dispensed into each feR tank 1 equipped with a canopy wing at 500 L, and added to a polymer solids concentration of 4 mg / L. Ions like silica collected Kawasaki industrial water was ₂ 7 m gSi0 2 ZL. In addition, because of the slime control Lumpur, it was 1 day 1 Kai添Roshi as hypochlorite! ^ The acid sodium becomes a 2 mg / L as C 1 _2.楊 fek was sent from the ume ^ K tank to the circulating water pit 3 with a retained water volume of 10 L by the feed pump 2. With the water level sensor and the electric transmission W sensor provided in the circulation zz pit,? It was managed at a lodging ratio of ₅ times. Circulation K is sent out from the circulation 7_K pit by the circulation pump 4 at 5 L / min, and heated through the soot pipe in u 5,

I was led to. The amount of water evaporated in the cooling tower was about 25 L / day, and the cooling in the cooling tower P was about 2 ° C. In the middle of piping from the Mf to the cooling tower, install an evaluation tube 7 made of SUS 3 04 with an inner diameter of 14 mm and a length of 10 Omm. 1 4 days ¾ The amount of dirt was determined from the difference in the weight of the language face tube.

Male example 1

The test was carried out using a copolymer (weight average molecular weight 10 0, 0 0 0) of a molar ratio of 6: 3 4 between atalinoleic acid and 2-acrylamido 2-methylpropanesulfonic acid. The amount of dirt adhered was 0.3 mg.

Example 2

The test was carried out using a copolymer (weight average molecular weight 10 0, 0 0 0) of atalinoleic acid and 2-atarylamide 2-methylpropanesulfonic acid having a molar ratio of 8: 1: 19. The amount of dirt adhered was 0.9 mg.

Narrow row 3

Experiments were carried out using a monolayer of atalic acid and isoprenenorephonic acid J; 80:20 copolymer (weight average, amount 7, 500). The amount of dirt adhered was 6.7 mg.

Difficult example 4

A test was conducted using a copolymer (weight average molecular weight 7,00,0) having a molar ratio of 6: 3: 7 of attalinoleic acid and vinylenosulfonic acid. The amount of dirt adhered was 6.1 mg.

Example 5

Experiments were conducted using a copolymer of maleic acid and styrene sulphonic acid having a molar ratio of 25:75 (weight average amount of 4,5,00). The amount of dirt adhered was 4.2 mg. Comparative Example 1

Tests were carried out using a worm polymer of sodium acrylate (weight average molecular weight 3,500). The amount of dirt adhered was 27.4 mg.

This stain was analyzed by Itojo. Acid contents solution content 53.5 wt% (of silica 45.5 by weight ^_0/0) was A1 ₂ 0 ₃ 12.4 wt ⁰ I strongly醒量23.0 wt ^_0/0.

Comparative Example 2

The test was conducted using a copolymer (weight average molecular weight of 3,000) having a molar ratio of 91: 9 of sodium acrylate and 3-aryoxy-2-hydroxypropanesulfonic acid. The amount of dirt adhered was 18.4 mg.

Comparative Example 3

The test was performed using a copolymer (weight average molecular weight 14,000) having a molar ratio of 92: 8 between acrylic acid and 2-acrylo-reamide-2-methylpropanesulfonic acid. The amount of dirt adhered is 16.2 mg.

Comparative Example 4

The test was carried out using a maleic acid warrant (weight average molecular weight 550). The amount of dirt adhered was 31.6 mg.

Comparative Example 5

The test was carried out using a copolymer of 80:20 molar ratio of maleic acid and 2-acryloreamido 2-methylpropane sulfonic acid (weight average molecular weight 2,000). The amount of dirt adhered was 28.9 m.

Comparative Example 6

A test was carried out using a copolymer (weight average molecular weight 14,500) having a molar ratio of maleic acid to isopylene of 1: 1. The amount of dirt adhered was 23.5 mg.

Table 1 shows the yarn destruction ratio and the sulfonic acid group / carboxyl adhesion amount of the monomers having sulfone cocoons of 1 to 5 and Comparative Examples 1 to 6. Table 1

D C

GO Reho:

Mono-carried monomer; ^ Shino 1¾

讓匕 (pig) (W / o) (Mode

麵 Row 1 acryl / 1 </ 2—acrylamido mono 2-methylpropane sulfonic acid 34 0.515 0.3 converse 2 acryl ^ 2-acrylamido mono 2-methylpropane sulfonic acid 19 0.235 0.9 m acryloisoprene sulfonic acid 20 0.250 6.7 麵Row 4 Ataryl ^ Bulsulfonic acid 37 0.587 6.1 Reference 5 Maleic acid / Styrene sulfonic acid 75 1.50 4.2 m Sodium acrylate 0 0 27.4 Column 2 Acrin! ^ Sodium / 3-allyloxy 2-hydroxypropanesulfonic acid 9 _ 0.099 18.4 Acrylino 2-acrylamido 2-methylpropanesulfonic acid 8 0.087 16.2

Maleic acid 0 0 31.6 Male 2-Atarylamide 2-Methylpropanesulfonic acid 20 0. 125 28.9 Malein // Isoptylene 0 0 23.5

As shown in Table 1, a copolymer of acrylic acid and a monomer having a sulfone ¾, wherein the yarn killing ratio of the monomer having a sulfone ¾ is 19 to 37 monole% In Examples 1 to 4, the amount of silica-based soil attached is small, and in particular, a copolymer of acrylic acid and 2-monoarylpropyl 2-sulfonic acid is used. :! ~ 2 is a very small amount of dirt. In addition, a copolymer having a carboxyl group and a sulfonating group, wherein a copolymer having a molar ratio of sulfonic acid group nocarboxyl group of 0.250 to 1.550 was added to circulating water. For 1-5, the amount of squeezing stains is small.

In contrast, in Comparative Example 1, Comparative Example 4, and Comparative Example 6 in which a warworm polymer or copolymer having only a force / repoxyl group and having no sulfone soot was added to circulating water, adhesion amount is large and be a copolymer of a monomer having a Atariru acid or a Natoriumu salt and a sulfonic acid group, a Itometsuhi 8-9 Monore ^_0/0 of the monomer having a Sunorehon Hokusatsu, sulfonic Hokusatsu Ζ In Comparative Example 2 and Comparative Example 3 in which a copolymer having a carboxyl group molar ratio of 0.0 8 7 to 0.0 9 9 was added, the amount of dirt adhered was large. Further, the composition ratio of the monomer having a sulfonic ^ ¾ even with 2 0 mole ^_0/0 is a copolymer of maleic acid, Sunorehon ^ S / Co molar ratio of the carboxyl group is 1 2 5 0. Even in Comparative Example 5 where the polymer was used, the amount of dirt adhered was large! Industrial applicability

According to the silica-based soil adhesion preventive agent and the anti-sticking method of the present invention, a copolymer having a (meth) acrylic acid unit and a monomer unit having a sulfone, the monomer unit having a sulfone group A copolymer having a yarn destruction ratio of more than 10 mol%, or a copolymer having a strong lpoxyl group and a sulfonic acid group, wherein the molar ratio of sulfonic acid group to carboxyl group is 0.15 to 2 By feeding the copolymer, which is 0, into the water system, it is possible to effectively prevent the adhesion of the soil of the sili force system, and to stabilize the system without causing problems in the cooling water system, the boiler water system, the tank system, etc. can do. The present invention can be applied to the prevention of adhesion of scouring soil generated in a reducing well of the ground.

Claims

The scope of the claims

1. The composition of a monomer unit having a sulfone group in a tE * polymer, which is a mixture of silica-based soils containing a copolymer having a (meth) acrylic acid unit and a monomer unit having a snorephone 纖An anti-sticking agent for scouring soils with a ratio exceeding 10%.

2. The anti-sticking agent for siri-type soils according to claim 1, wherein the monomer having sulfonation is 2-acrylamide-1,2-methylpropane sulfonic acid.

3. An adhesion preventive agent for silicic acid-based soils containing a copolymer having a carboxyl group and a sulfone group, wherein the molar ratio of the sulfone group is 0.1 to 2.0. An anti-sticking agent for scouring system stains.

4. A copolymer having a (meth) acrylic acid unit and a monomer unit having sulfone sleep in the circulation 7K, and the JJ¾¾ ratio of the monomer unit having a sulfone group in the lilt self-copolymer is 1

Prevention of adhesion of silica-based soils with the use of a copolymer exceeding 0 mol% as glue.

5. The method for preventing adhesion of scouring-type soils according to claim 4, wherein the monomer having sulfone wisteria is 2-acrylamido-2-methylpropanesulfonic acid.

6. Add a copolymer having a strong lpoxyl group and a sulfone ring to the circulating water, wherein the molar ratio of sulfonic acid group Z carboxyl group is O.15 to 2.0. Siri force system that uses the number of glues as it is.