JP2005230617A - Silica-based scale inhibitor and silica-based scale inhibition method - Google Patents
Silica-based scale inhibitor and silica-based scale inhibition method Download PDFInfo
- Publication number
- JP2005230617A JP2005230617A JP2004040111A JP2004040111A JP2005230617A JP 2005230617 A JP2005230617 A JP 2005230617A JP 2004040111 A JP2004040111 A JP 2004040111A JP 2004040111 A JP2004040111 A JP 2004040111A JP 2005230617 A JP2005230617 A JP 2005230617A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- water
- based scale
- scale inhibitor
- substituents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、冷却水系やボイラ水系などのシリカ系スケールの防止に有効なシリカ系スケール防止剤及びシリカ系スケール防止方法に関する。 The present invention relates to a silica-based scale inhibitor and a silica-based scale prevention method that are effective in preventing silica-based scales such as cooling water systems and boiler water systems.
冷却水系、ボイラ水系などの水と接触する伝熱面、配管内ではスケール障害が発生する。特に、開放循環式冷却水系において、省資源、省エネルギーの立場から、冷却水の系外への排出（ブロー）を少なくして高濃縮運転が行われる場合、冷却水中に溶存する塩類が濃縮されるとともに、難溶性の塩が析出してスケール化する。生成したスケールは、熱効率の低下、配管の閉塞など、ボイラや熱交換器などの運転に重大な障害を引き起こす。 Scale failure occurs in heat transfer surfaces and piping that come into contact with water such as cooling water systems and boiler water systems. In particular, in an open circulation type cooling water system, from the standpoint of resource saving and energy saving, when highly concentrated operation is performed with less discharge (blow) of cooling water out of the system, salts dissolved in the cooling water are concentrated. At the same time, a sparingly soluble salt precipitates and scales. The generated scale causes serious obstacles to the operation of boilers and heat exchangers, such as a decrease in thermal efficiency and blockage of piping.
水系に生成するスケール種としては、炭酸カルシウム、硫酸カルシウム等のカルシウム系スケールや、シリカ（ケイ酸）系スケール等があるが、このうち、シリカ系スケールに対しては、アクリル酸系やマレイン酸系の水溶性ポリマーや、ホスホン酸を有効成分とするスケール防止剤が用いられている。 Scale species generated in water include calcium-based scales such as calcium carbonate and calcium sulfate, and silica (silicic acid) -based scales. Among these, acrylic acid-based and maleic acid are used for silica-based scales. A water-soluble polymer and a scale inhibitor containing phosphonic acid as an active ingredient are used.
また、特開２００２−５９１９３号公報には、γ−ブチロラクトンのような環状エステル化合物を用いることが記載されている。
しかしながら、従来提案されているシリカ系スケール防止剤では、十分に満足し得るスケール防止効果が得られてはおらず、また、特開２００２−５９１９３号公報に記載されるγ−ブチロラクトンのような環状エステル化合物はスケール防止効果においては優れるものの、スケール防止剤自体によるＣＯＤの増加等の水系の汚染やスライム障害の問題が懸念されることから、水系汚染やスライム障害を引き起こすことなく、シリカ系スケールをより一層効果的に防止し得るシリカ系スケール防止剤の開発が望まれている。 However, with the conventionally proposed silica-based scale inhibitors, a sufficiently satisfactory scale prevention effect has not been obtained, and cyclic esters such as γ-butyrolactone described in JP-A-2002-59193 are not obtained. Although the compound is excellent in scale prevention effect, there is a concern about the problem of water pollution and slime damage such as increase in COD due to the scale inhibitor itself, so silica scale is more effective without causing water pollution and slime damage. Development of a silica-based scale inhibitor that can be more effectively prevented is desired.
従って、本発明は、冷却水系、ボイラ水系などで生成するシリカ系スケールの付着防止に対して優れた効果を発揮し、しかも水系汚染やスライム障害の問題もないシリカ系スケール防止剤及びシリカ系スケール防止方法を提供することを目的とする。 Therefore, the present invention exhibits an excellent effect for preventing adhesion of silica-based scales produced in cooling water systems, boiler water systems, and the like, and also has no problems of water-based contamination and slime damage. An object is to provide a prevention method.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、鎖状水溶性ポリエステル化合物が、シリカ系スケールの防止効果に優れ、水系の汚染性も低いことを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the chain water-soluble polyester compound is excellent in the effect of preventing silica-based scale and has low water-based contamination. Based on this, the present invention has been completed.
即ち、本発明のシリカ系スケール防止剤は、エステル基を２個以上有する鎖状水溶性ポリエステル化合物を含むことを特徴とする。 That is, the silica-based scale inhibitor of the present invention includes a chain water-soluble polyester compound having two or more ester groups.
また、本発明のシリカ系スケール防止方法は、このような本発明のシリカ系スケール防止剤を、水系に添加することを特徴とする。 The silica-based scale prevention method of the present invention is characterized in that such a silica-based scale inhibitor of the present invention is added to an aqueous system.
本発明のシリカ系スケール防止剤及びシリカ系スケール防止方法によれば、水系の汚染を引き起こすことなく、冷却水系、ボイラ水系等の各種水系のシリカ系スケールを有効に防止して、熱効率の低下、配管閉塞等のスケール障害を未然に防止し、水系の安定な運転を図ることができる。 According to the silica-based scale inhibitor and the silica-based scale prevention method of the present invention, without causing water-based contamination, various water-based silica scales such as a cooling water system and a boiler water system are effectively prevented, and thermal efficiency is reduced. Scale failures such as piping blockage can be prevented and stable operation of the water system can be achieved.
以下に本発明のシリカ系スケール防止剤及びシリカ系スケール防止方法の実施の形態を詳細に説明する。 Hereinafter, embodiments of the silica-based scale inhibitor and the silica-based scale prevention method of the present invention will be described in detail.
まず、本発明で用いる鎖状水溶性ポリエステル化合物について説明する。 First, the chain water-soluble polyester compound used in the present invention will be described.
この鎖状水溶性ポリエステル化合物はエステル基を２個以上有する鎖状の水溶性ポリエステル化合物である。なお、本発明において、「ポリエステル化合物」とは必ずしも高分子化合物を指すものではなく、ジエステル、トリエステル等の低分子化合物をも包含するものである。 This chain water-soluble polyester compound is a chain water-soluble polyester compound having two or more ester groups. In the present invention, the “polyester compound” does not necessarily indicate a high molecular compound, but also includes low molecular compounds such as diesters and triesters.
この鎖状水溶性ポリエステル化合物としては、特に下記一般式（Ｉ）で表される構造部分を有するか、或いは、下記一般式（II）又は（III）で表されるものが好ましい。 As the chain water-soluble polyester compound, those having a structural portion represented by the following general formula (I) or those represented by the following general formula (II) or (III) are particularly preferable.
一般式（II）、（III）において、Ｄは１種類以上の置換基を有していても良い炭素数１０以下のアルキレン基、又は１種類以上の置換基を有していても良いフェニレン基を表し、Ｅは１種類以上の置換基を有していても良いアルキル基又は１種類以上の置換基を有していても良いフェニル基を表す。）
In the general formulas (II) and (III), D is an alkylene group having 10 or less carbon atoms which may have one or more substituents, or a phenylene group which may have one or more substituents. And E represents an alkyl group optionally having one or more substituents or a phenyl group optionally having one or more substituents. )
上記一般式（Ｉ）及び（II）、（III）において、Ａ及びＤのアルキレン基又はフェニレン基が有し得る置換基としては、スルホン酸基、カルボキシル基、アルキレンオキサイド、水酸基、アミノ基等の親水基が挙げられる。 In the general formulas (I), (II), and (III), examples of the substituent that the alkylene group or phenylene group of A and D may have include a sulfonic acid group, a carboxyl group, an alkylene oxide, a hydroxyl group, and an amino group. A hydrophilic group is mentioned.
Ａ及びＤのアルキレン基としては、側鎖を有する分岐アルキレン基であっても直鎖アルキレン基であっても良い。Ａ及びＤのアルキレン基として好ましくは炭素数１〜４のアルキレン基が挙げられる。 The alkylene group for A and D may be a branched alkylene group having a side chain or a linear alkylene group. The alkylene group of A and D is preferably an alkylene group having 1 to 4 carbon atoms.
一般式（II）、（III）において、Ｅのアルキル基又はフェニル基が有し得る置換基としては、スルホン基、カルボキシル基、アルキレンオキサイド、水酸基、アミノ基などの親水基が挙げられる。 In the general formulas (II) and (III), examples of the substituent that the alkyl group or phenyl group of E may have include a hydrophilic group such as a sulfone group, a carboxyl group, an alkylene oxide, a hydroxyl group, and an amino group.
Ｅのアルキル基として好ましくは炭素数１〜４のアルキル基が挙げられる。 The alkyl group for E is preferably an alkyl group having 1 to 4 carbon atoms.
また、一般式（Ｉ）において、ｎは３〜１０００の整数であるが、好ましくは３〜２００であり、本発明に係る鎖状水溶性ポリエステル化合物は、分子量が１００〜１０００程度のものであることが好ましい。この鎖状水溶性ポリエステル化合物の分子量が１００未満では揮発性が高く、１０００を超えると溶解性が悪くなる。 In general formula (I), n is an integer of 3 to 1000, preferably 3 to 200, and the chain water-soluble polyester compound according to the present invention has a molecular weight of about 100 to 1000. It is preferable. When the molecular weight of the chain water-soluble polyester compound is less than 100, the volatility is high, and when it exceeds 1000, the solubility is deteriorated.
なお、本発明のシリカ系スケール防止剤による処理はｐＨ２．５〜１１の条件で行うことが好ましく、従って、このようなｐＨに調整するために、必要に応じて、酸又はアルカリのｐＨ調整剤を添加しても良い。 In addition, it is preferable to perform the process by the silica type scale inhibitor of this invention on the conditions of pH2.5-11, Therefore, In order to adjust to such pH, as needed, it is an acid or alkali pH adjuster. May be added.
本発明のシリカ系スケール防止剤は、冷却水系、ボイラ水系などの水質条件及び運転条にかかわりなく使用することができる。本発明のシリカ系スケール防止剤は、冷却水系、ボイラ水系などにおいて、循環水又は補給水などに添加して使用することができる。本発明のシリカ系スケール防止剤を添加する場所及び添加方法には特に制限はなく、使用する水系において、任意の濃度に調製した水溶液として、任意の箇所において添加することができる。 The silica scale inhibitor of the present invention can be used regardless of water quality conditions and operating conditions such as cooling water system and boiler water system. The silica-based scale inhibitor of the present invention can be used by adding to circulating water or makeup water in a cooling water system, a boiler water system, and the like. There is no restriction | limiting in particular in the place and addition method in which the silica type scale inhibitor of this invention is added, It can add in arbitrary places as aqueous solution adjusted to arbitrary density | concentrations in the aqueous system to be used.
本発明のシリカ系スケール防止剤の添加量は、添加する水系の水質、設備の運転条件などに応じて適宜選択することができるが、通常は水中の前記鎖状水溶性ポリエステル化合物濃度が１０〜１００ｍｇ／Ｌとなるよう添加することが好ましく、１０〜５０ｍｇ／Ｌとなるよう添加することがより好ましい。 The addition amount of the silica-based scale inhibitor of the present invention can be appropriately selected according to the quality of the aqueous system to be added, the operating conditions of the equipment, etc., but usually the concentration of the chain water-soluble polyester compound in water is 10 to 10. It is preferable to add so that it may become 100 mg / L, and it is more preferable to add so that it may become 10-50 mg / L.
このような本発明のシリカ系スケール防止剤は、必要に応じて他のスケール防止剤、防食剤、殺菌剤、スライム防止剤などと併用することができる。本発明のシリカ系スケール防止剤を他の薬剤と併用する場合、こられの薬剤を予め混合して一液型としても良く、それぞれを別個に添加しても良い。 Such a silica-based scale inhibitor of the present invention can be used in combination with other scale inhibitors, anticorrosives, bactericides, slime inhibitors, and the like as necessary. When the silica-based scale inhibitor of the present invention is used in combination with other chemicals, these chemicals may be mixed in advance to form a one-pack type, or each may be added separately.
以下に実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
実施例１〜４、比較例１〜７
ＭｇＳＯ４・７Ｈ２Ｏを４００ｍｇ／Ｌ（マグネシウム硬度：２００ｍｇ−ＣａＣＯ３／Ｌ）、ｍＮａ２Ｏ・ｎＳｉＯ２を２１０ｍｇ／Ｌ（ＳｉＯ２濃度：２１０ｍｇ−ＳｉＯ２／Ｌ）、及びＮａＨＣＯ３を２００ｍｇ／Ｌ（Ｍアルカリ度：２００ｍｇ−ＣａＣＯ３／Ｌ）となるように純水に溶解して試験液を調製した。この試験液に表１に示すスケール防止剤を５０ｍｇ／Ｌ添加し（ただし、比較例７ではスケール防止剤を添加せず）、ｐＨを９．０に調整して試験に供した。
Examples 1-4, Comparative Examples 1-7
MgSO 4 · 7H 2 O 400 mg / L (magnesium hardness: 200 mg-CaCO 3 / L), mNa 2 O · nSiO 2 210 mg / L (SiO 2 concentration: 210 mg-SiO 2 / L), and NaHCO 3 200 mg / L (M alkalinity: 200 mg-CaCO 3 / L) was dissolved in pure water to prepare a test solution. 50 mg / L of the scale inhibitor shown in Table 1 was added to this test solution (however, the scale inhibitor was not added in Comparative Example 7), and the pH was adjusted to 9.0 for use in the test.
図１はスケール付着試験に用いた装置の概略構成を示す系統図である。１はステンレス製の伝熱チューブであり、ヒーター２による加熱で９０℃に制御されている。この伝熱チューブの外側に循環水槽３からの試験液を循環ポンプ４により、電磁弁５を介して流速０．５ｍ／秒で循環させた。６は冷却コイルであり、循環水槽３内の水は水温３０℃に冷却される。この循環水槽３の滞留時間は２４時間である。また、この循環水槽３には補給水槽７から補給水ポンプ８により補給水が供給される。
FIG. 1 is a system diagram showing a schematic configuration of an apparatus used for a scale adhesion test. Reference numeral 1 denotes a stainless steel heat transfer tube, which is controlled to 90 ° C. by heating with the heater 2. The test solution from the circulating water tank 3 was circulated through the electromagnetic valve 5 at a flow rate of 0.5 m / sec by the circulation pump 4 outside the heat transfer tube. A
通水を４８時間行った後、伝熱チューブ１を取り出して乾燥し、付着物（スケール）を採取し、その重量を測定し、結果を表１に示した。この付着物量が少ない程、スケール防止効果に優れる。 After passing water through for 48 hours, the heat transfer tube 1 was taken out and dried, the deposit (scale) was collected, the weight was measured, and the results are shown in Table 1. The smaller the amount of deposits, the better the scale prevention effect.
また、各例で用いたスケール防止剤を超純水中に５ｐｐｍ添加し、そのＣＯＤＭｎ値をＪＩＳ Ｋ ０１０２１７に従って分析し、その結果を表１に示した。このＣＯＤＭｎ値が低い程、水系に対する汚染性が低く、スライム障害を起こしにくい。 Further, 5 ppm of the scale inhibitor used in each example was added to ultrapure water, and the COD Mn value was analyzed according to JIS K 010217. The results are shown in Table 1. The lower the COD Mn value, the lower the contamination with respect to the water system and the less likely to cause slime damage.
表１より、本発明に係る鎖状水溶性ポリエステル化合物及びジエステル（エチレングリコール）は、スケール防止効果においてポリアクリル酸などの従来のスケール防止剤よりも優れる。また、γ−ブチロラクトンとスケール防止効果においてほぼ同等であるが、ＣＯＤＭｎ、ＢＯＤ値において優れていることが分かる。 From Table 1, the chain | strand water-soluble polyester compound and diester (ethylene glycol) which concern on this invention are superior to conventional scale inhibitors, such as polyacrylic acid, in the scale prevention effect. Further, it is almost the same as γ-butyrolactone in the scale prevention effect, but it is understood that it is excellent in COD Mn and BOD values.
本発明は、冷却水系、ボイラ水系、地熱発電所等の各種水系のシリカ系スケールの防止に有効である。 The present invention is effective in preventing silica scales of various water systems such as cooling water systems, boiler water systems, and geothermal power plants.
１ 伝熱チューブ
２ ヒーター
３ 循環水槽
４ 循環ポンプ
５ 電磁弁
６ 冷却コイル
７ 補給水槽
８ 補給水ポンプ
1 Heat Transfer Tube 2 Heater 3 Circulating Water Tank 4 Circulating Pump 5
Claims (4)
一般式（II）、（III）において、Ｄは１種類以上の置換基を有していても良い炭素数１０以下のアルキレン基、又は１種類以上の置換基を有していても良いフェニレン基を表し、Ｅは１種類以上の置換基を有していても良いアルキル基又は１種類以上の置換基を有していても良いフェニル基を表す。） The chain water-soluble polyester compound according to claim 1, wherein the chain water-soluble polyester compound has a structural portion represented by the following general formula (I), or is represented by the following general formula (II) or (III) Silica scale inhibitor.
In general formulas (II) and (III), D is an alkylene group having 10 or less carbon atoms which may have one or more substituents, or a phenylene group which may have one or more substituents. And E represents an alkyl group optionally having one or more substituents or a phenyl group optionally having one or more substituents. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004040111A JP4479265B2 (en) | 2004-02-17 | 2004-02-17 | Silica-based scale inhibitor and silica-based scale prevention method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004040111A JP4479265B2 (en) | 2004-02-17 | 2004-02-17 | Silica-based scale inhibitor and silica-based scale prevention method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005230617A true JP2005230617A (en) | 2005-09-02 |
| JP4479265B2 JP4479265B2 (en) | 2010-06-09 |
Family
ID=35014120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004040111A Expired - Fee Related JP4479265B2 (en) | 2004-02-17 | 2004-02-17 | Silica-based scale inhibitor and silica-based scale prevention method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4479265B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013503741A (en) * | 2009-09-02 | 2013-02-04 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for inhibiting the deposition of silica and / or silicate compounds in aqueous systems |
-
2004
- 2004-02-17 JP JP2004040111A patent/JP4479265B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013503741A (en) * | 2009-09-02 | 2013-02-04 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for inhibiting the deposition of silica and / or silicate compounds in aqueous systems |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4479265B2 (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2943022T3 (en) | Scale removal method for steam generation installations | |
| JPS58177479A (en) | Method of controlling corrosion and sedimentation in aqueous system and composition therefor | |
| ES2766763T3 (en) | Method for removing scale in steam generation facilities | |
| KR20130091317A (en) | Anticorrosive for boiler | |
| KR910018315A (en) | Methods of inhibiting deposition and corrosion in water-using devices | |
| ES2378245T3 (en) | Method to stabilize a motor coolant concentrate and prevent the formation of hard water salt with dilution | |
| US5332505A (en) | Method for inhibiting silica and silicate deposition | |
| JP4479265B2 (en) | Silica-based scale inhibitor and silica-based scale prevention method | |
| JP6256538B2 (en) | Boiler deoxygenating agent and boiler water-based deoxygenating method | |
| JP2916721B2 (en) | Coolant composition | |
| US20050023506A1 (en) | Organic corrosion inhibitors and corrosion control methods for water systems | |
| KR101514715B1 (en) | Composition for removing scale and rust | |
| JP6401578B2 (en) | Copper anticorrosion composition and copper anticorrosion method | |
| JP5842293B2 (en) | Anti-paining agent and anti-paining method | |
| JP6314560B2 (en) | Water treatment method for steam generating equipment | |
| JP5978711B2 (en) | Iron corrosion control method | |
| JP5879699B2 (en) | Corrosion prevention method for boiler water supply system | |
| KR100571660B1 (en) | Composition material of antifreeze | |
| JP2006233287A (en) | Corrosion-preventing composition and corrosion-preventing method | |
| JP2006274337A (en) | Treatment agent and treatment method for boiler water | |
| JP2008248303A (en) | Pitting corrosion inhibitor for circulating cooling water system including copper base material, and method for inhibiting pitting corrosion | |
| JP2002059193A (en) | Method of preventing silica-base scale | |
| JP2001310191A (en) | Method for treating aqueous system | |
| JP2001049471A (en) | Water base corrosion inhibiting method | |
| JP2013067830A (en) | Corrosion inhibit method of economizer in boiler |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070131 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091222 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100127 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100223 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100308 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130326 Year of fee payment: 3 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130326 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |