JPS6248560B2 - - Google Patents
Info
- Publication number
- JPS6248560B2 JPS6248560B2 JP57121349A JP12134982A JPS6248560B2 JP S6248560 B2 JPS6248560 B2 JP S6248560B2 JP 57121349 A JP57121349 A JP 57121349A JP 12134982 A JP12134982 A JP 12134982A JP S6248560 B2 JPS6248560 B2 JP S6248560B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- same
- acid represented
- different
- phosphonic acid
- 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.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002455 scale inhibitor Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- -1 Aminodimethylphosphomonoethylphosphonic acid Chemical compound 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229960002449 glycine Drugs 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- MJPWXCPGHYETKV-UHFFFAOYSA-N (3-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound OCCC(P(O)(O)=O)P(O)(O)=O MJPWXCPGHYETKV-UHFFFAOYSA-N 0.000 description 1
- OOOLSJAKRPYLSA-UHFFFAOYSA-N 2-ethyl-2-phosphonobutanedioic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)CC(O)=O OOOLSJAKRPYLSA-UHFFFAOYSA-N 0.000 description 1
- ROBBYOHKXYELRG-UHFFFAOYSA-N 2-phosphonohexane-1,2,4-tricarboxylic acid Chemical compound CCC(C(O)=O)CC(P(O)(O)=O)(C(O)=O)CC(O)=O ROBBYOHKXYELRG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- LGERWORIZMAZTA-UHFFFAOYSA-N silicon zinc Chemical compound [Si].[Zn] LGERWORIZMAZTA-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】
従来から、亜鉛びき鋼管（内表面が亜鉛メツキ
された鋼管）は、防食を目的として水道配管用に
供されていたが、最近、入手し易いという点か
ら、ボイラ復水回収系にも多用されるようになつ
てきた。[Detailed Description of the Invention] Conventionally, galvanized steel pipes (steel pipes whose inner surfaces are galvanized) have been used for water piping for the purpose of corrosion prevention, but recently they have been used for boiler restoration because they are easily available. It has also come to be widely used in water recovery systems.
しかしながら、この配管をボイラ復水回収系に
用いた場合には、水中へ溶出する亜鉛イオンの作
用により、以下のような問題が生ずる。 However, when this piping is used in a boiler condensate recovery system, the following problems occur due to the action of zinc ions eluted into water.
即ち、オイルシヨツク以後、省エネルギー対策
の一環として、復水回収率の増大及び濃縮倍率の
増大（通常、10〜15倍）が図られているが、この
際、溶出した亜鉛イオンを多量に含む復水が再度
給水として供給され、しかも、ブロー率が低く
（濃縮率が高く）設定されるため、亜鉛イオンと
給水中に存在するシリカ等とが反応してケイ素亜
鉛、塩基性炭酸亜鉛、水酸化亜鉛等のスケールを
生成し、これらが大量にボイラ内に付着する。そ
の結果、熱交換率の低下、配管の閉塞、熱交換器
の閉塞に基づく暴発等の不都合な事態を招来する
おそれがあつた。同様の問題は、従来から使用さ
れている亜鉛含有合金（例えば、アルミニウム黄
銅）を材質としたボイラ用配管についてもみられ
た。 In other words, since oil shock, as part of energy-saving measures, efforts have been made to increase the condensate recovery rate and increase the concentration ratio (usually 10 to 15 times). Water is supplied as feed water again, and the blow rate is set low (concentration rate is high), so zinc ions and silica etc. present in the feed water react to form zinc silicon, basic zinc carbonate, and hydroxide. Generates scales such as zinc, which adhere in large quantities inside the boiler. As a result, there was a risk of causing inconvenient situations such as a decrease in heat exchange efficiency, blockage of piping, and explosion due to blockage of the heat exchanger. Similar problems have also been observed in boiler piping made of conventionally used zinc-containing alloys (eg, aluminum brass).
従つて、ボイラ復水回収系に亜鉛びき鋼管を適
用した場合には、上記した不都合を解消しなけれ
ばならないにもかかわらず、現在迄、ボイラ水中
の亜鉛イオンに起因するスケール発生の抑制策は
何ら講じられていなかつた。 Therefore, when galvanized steel pipes are applied to boiler condensate recovery systems, the above-mentioned disadvantages must be resolved, but to date, no measures have been taken to suppress scale generation caused by zinc ions in boiler water. Nothing was taught.
本発明は、ボイラ給水に添加して、ボイラ水系
内の亜鉛イオンに起因するスケールの生成を抑制
せしめる新規なスケール防止剤を提供することを
目的とする。 An object of the present invention is to provide a novel scale inhibitor that can be added to boiler feed water to suppress the formation of scale caused by zinc ions in the boiler water system.
本発明のスケール防止剤は、
次式（）：
（式中、X1〜X3及びY1〜Y3は、各々、同一もしく
は異なつていてもよく、水素原子、炭素数１〜５
の低級アルキル基を表わし；Z1〜Z6は、各々、同
一もしくは異なつていてもよく、水素原子、アル
カリ金属原子、アンモニウムを表わす。）
で示されるホスホン酸；
次式（）：
［式中、R1、R2及びR4は、各々、同一もしくは異
なつていてもよく、次の基(A)：
（X1、Y1、Z1及びZ2は、前記（）式の場合と同
じ意味を有する。）
を表わし；R3は、上記した基(A)、炭素数１〜５
の低級アルキル基を表わし；ｎは１〜３の整数を
表わす。］
で示されるホスホン酸；
次式（）：
（式中、Ｘは水素原子、炭素数１〜５の低級アル
キル基を表わし；Ｙは水素原子、炭素数１〜５の
低級アルキル基、水酸基、アンモニウムを表わ
し；Z1〜Z4は前記（）式の場合と同じ意味を有
する。）
で示されるホスホン酸；
次式（）：
（式中、R1〜R6は、各々、同一もしくは異つてい
てもよく、水素原子、炭素数１〜５の低級アルキ
ル基、カルボキシル基を表わし；X1〜X3及び
Z1、Z2は前記（）式の場合と同じ意味を有す
る。）
で示されるホスホン酸；
次式（）：
（式中、X1、X2は各々同一もしくは異なつていて
もよく、Ｈ、−CH2−CH2−OHまたは−CH2−
COOZ2を表わし；Z1、Z2は前記（）式の場合
と同じ意味を有する。）
で示されるα−アミノカルボン酸もしくは
次式（）：
（式中、X1、X2、X3及びX4は、各々同一もしくは
異なつていてもよく、−CH2−CH2−OH、−CH2
−COOZ1を表わし、ｎは１〜３の整数を表わ
し、Z1は前記（）式の場合と同じ意味を有す
る。）
で示されるα−アミノカルボン酸；
又はこれらの水溶性塩から選ばれる１種もしくは
２種以上の化合物から成る亜鉛びき鋼管又は亜鉛
を含む合金からなることを特徴とする。 The scale inhibitor of the present invention has the following formula (): (In the formula, X 1 to X 3 and Y 1 to Y 3 may be the same or different, and each has a hydrogen atom, a carbon number of 1 to 5
represents a lower alkyl group; Z 1 to Z 6 may each be the same or different and represent a hydrogen atom, an alkali metal atom, or ammonium. ) Phosphonic acid represented by the following formula (): [In the formula, R 1 , R 2 and R 4 may each be the same or different, and the following group (A): (X 1 , Y 1 , Z 1 and Z 2 have the same meanings as in the above formula ()); R 3 is the group (A) described above, and has 1 to 5 carbon atoms.
represents a lower alkyl group; n represents an integer of 1 to 3; ] Phosphonic acid represented by the following formula (): (In the formula, X represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms; Y represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or ammonium; Z 1 to Z 4 are the above-mentioned ( ) Phosphonic acid represented by the following formula (): (In the formula, R 1 to R 6 may be the same or different, and each represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a carboxyl group ;
Z 1 and Z 2 have the same meanings as in the above formula (). ) Phosphonic acid represented by the following formula (): (In the formula, X 1 and X 2 may be the same or different, H, -CH 2 -CH 2 -OH or -CH 2 -
represents COOZ 2 ; Z 1 and Z 2 have the same meanings as in the above formula (). ) or α-aminocarboxylic acid represented by the following formula (): (In the formula, X 1 , X 2 , X 3 and X 4 may be the same or different, respectively, -CH 2 -CH 2 -OH, -CH 2
-COOZ 1 , n represents an integer of 1 to 3, and Z 1 has the same meaning as in the above formula (). It is characterized by being made of a galvanized steel pipe or an alloy containing zinc, comprising one or more compounds selected from α-aminocarboxylic acids represented by the following:
式（）で示されるホスホン酸もしくはその水
溶性塩としては、次のものが例示される。 Examples of the phosphonic acid represented by formula () or its water-soluble salt include the following.
(1) アミノトリメチルホスホン酸及びそのナトリ
ウム、カリウム、アンモニウム塩
(2) アミノジメチルホスホモノエチルホスホン酸
及びそのナトリウム、カリウム、アンモニウム
塩
式（）で示されるホスホン酸もしくはその水
溶性塩としては、次のものが例示される。(1) Aminotrimethylphosphonic acid and its sodium, potassium, and ammonium salts (2) Aminodimethylphosphomonoethylphosphonic acid and its sodium, potassium, and ammonium salts Phosphonic acids represented by formula () or their water-soluble salts include the following: The following are exemplified.
(1) エチレンジアミンテトラメチルホスホン酸及
びそのナトリウム、カリウム、アンモニウム塩
(2) ジエチレントリアミンペンタメチルホスホン
酸及びそのナトリウム、カリウム、アンモニウ
ム塩
(3) トリエチレンテトラアミンヘキサメチルホス
ホン酸及びそのナトリウム、カリウム、アンモ
ニウム塩
式（）で示されるホスホン酸もしくはその水
溶性塩としては、次のものが例示される。(1) Ethylenediaminetetramethylphosphonic acid and its sodium, potassium, and ammonium salts (2) Diethylenetriaminepentamethylphosphonic acid and its sodium, potassium, and ammonium salts (3) Triethylenetetraaminehexamethylphosphonic acid and its sodium, potassium, and ammonium salts Formula ( ) Examples of the phosphonic acid or water-soluble salt thereof include the following.
(1) ヒドロキシエチリデンジホスホン酸及びその
ナトリウム、カリウム、アンモニウム塩
(2) ヒドロキシプロピリデンジホスホン酸及びそ
のナトリウム、カリウム、アンモニウム塩
式（）で示されるホスホン酸もしくはその水
溶性塩としては、次のものが例示できる。(1) Hydroxyethylidene diphosphonic acid and its sodium, potassium, and ammonium salts (2) Hydroxypropylidene diphosphonic acid and its sodium, potassium, and ammonium salts Phosphonic acids represented by formula () or their water-soluble salts include the following: Examples include:
(1) １・２・４−トリカルボキシブタン−２−ホ
スホン酸及びそのナトリウム、カリウム、アン
モニウム塩
(2) １・２−ジカルボキシブタン−２−ホスホン
酸及びそのナトリウム、カリウム、アンモニウ
ム塩
(3) １・２・４−トリカルボキシヘキサン−２−
ホスホン酸及びそのナトリウム、カリウム、ア
ンモニウム塩
式（）で示されるα−アミノカルボン酸もし
くはその水溶性塩としては、アミノ酢酸、イミノ
ジ酢酸、Ｎ−（β−ヒドロキシエチル）−アミノジ
酢酸、Ｎ・Ｎ−ジ（β−ヒドロキシエチル）−グ
リシン、ニトリロトリ酢酸もしくはそれらのナト
リウム、カリウム、アンモニウム塩が例示され
る。(1) 1,2,4-tricarboxybutane-2-phosphonic acid and its sodium, potassium, and ammonium salts (2) 1,2-dicarboxybutane-2-phosphonic acid and its sodium, potassium, and ammonium salts (3) ) 1,2,4-tricarboxyhexane-2-
Phosphonic acid and its sodium, potassium, ammonium salts α-aminocarboxylic acids represented by formula () or water-soluble salts thereof include aminoacetic acid, iminodiacetic acid, N-(β-hydroxyethyl)-aminodiacetic acid, N.N. -di(β-hydroxyethyl)-glycine, nitrilotriacetic acid, or their sodium, potassium, or ammonium salts are exemplified.
式（）で示されるα−アミノカルボン酸もし
くはその水溶性塩としては、エチレンジアミンテ
トラ酢酸、Ｎ−（β−ヒドロキシエチル）−エチレ
ンジアミントリ酢酸、ジエチレントリアミンペン
タ酢酸、トリエチレンテトラミンヘキサ酢酸もし
くはそれらのナトリウム、カリウム、アンモニウ
ム塩が例示される。 The α-aminocarboxylic acid represented by formula () or its water-soluble salt includes ethylenediaminetetraacetic acid, N-(β-hydroxyethyl)-ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, or sodium thereof; Examples include potassium and ammonium salts.
本発明の防止剤は、ボイラ給水に所定量添加さ
れて、スケール防止効果を発揮する。その添加量
は、ボイラ水中の亜鉛濃度によつて異なるが、通
常0.1〜1000ppm、好ましくは10〜100ppmの範囲
に設定される。0.1ppm未満の場合には、亜鉛ス
ケールに対する封鎖作用が不十分となり、
1000ppmを超える場合には効果がほぼ一定し、
不経済となる。ボイラ給水に添加するに際して
は、本発明の防止剤を、単独でもしくは２種以上
適宜に混合してもよい。また、これらを水に溶解
して水溶液とした後、添加してもよい。更には、
腐食、スケール、スラツジ、PH、硬度等を調整す
るために常用される添加剤、例えば、ヒドラジ
ン、水酸化ナトリウム、リン酸ナトリウム、ポリ
アクリル酸ナトリウムが添加された水系に本発明
防止剤を添加してもよく、この場合にあつても、
本発明防止剤の効果は何ら損なわれない。 The inhibitor of the present invention exhibits a scale prevention effect when added in a predetermined amount to boiler feed water. The amount added varies depending on the zinc concentration in the boiler water, but is usually set in the range of 0.1 to 1000 ppm, preferably 10 to 100 ppm. If it is less than 0.1ppm, the sequestration effect against zinc scale will be insufficient,
When it exceeds 1000ppm, the effect is almost constant,
It becomes uneconomical. When added to boiler feed water, the inhibitor of the present invention may be used alone or in combination of two or more. Alternatively, these may be added after being dissolved in water to form an aqueous solution. Furthermore,
The inhibitor of the present invention is added to an aqueous system containing additives commonly used to adjust corrosion, scale, sludge, pH, hardness, etc., such as hydrazine, sodium hydroxide, sodium phosphate, and sodium polyacrylate. Even in this case,
The effect of the inhibitor of the present invention is not impaired in any way.
尚、本発明の防止剤のスケール生成に対する抑
制効果は、主としてキレート形成による亜鉛イオ
ンの封鎖作用に起因するものと推測される。 It is assumed that the inhibitory effect of the inhibitor of the present invention on scale formation is mainly due to the sequestration effect of zinc ions through chelate formation.
以上の説明は、ボイラ水系を対象としたもので
あるが、本発明のスケール防止剤は、ボイラ水系
に適用する。 Although the above description is directed to boiler water systems, the scale inhibitor of the present invention is applied to boiler water systems.
本発明のスケール防止剤を用いれば、ボイラ水
系中の亜鉛イオンに起因するスケールの生成を十
分に抑制することが可能となる。しかも、180〜
250℃の温度域において使用しても、スケールの
生成を抑制する効果は安定して発揮されるので、
ボイラの高濃縮運転等の省エネルギー運転を行な
つても、スケールによる各種弊害が回避されるこ
ととなり、その工業的価値は極めて大きい。 By using the scale inhibitor of the present invention, it becomes possible to sufficiently suppress the formation of scale caused by zinc ions in the boiler water system. Moreover, 180~
Even when used in a temperature range of 250℃, the effect of suppressing scale formation is stably demonstrated.
Even if energy-saving operation such as high concentration operation of the boiler is performed, various harmful effects caused by scale can be avoided, and its industrial value is extremely large.
以下に、実施例を掲げ、本発明のスケール防止
剤の効果を明らかにする。 Examples are given below to clarify the effects of the scale inhibitor of the present invention.
実施例
圧力10Kgｆ／cm2、温度180℃、保有水量4.75
、ブロー水量1.16／hrのテストボイラ条件下
で試験を行ない、テストチユーブ（SB−42使
用、内表面積175cm2）内に付着したスケール量を
測定した。Example Pressure 10Kgf/cm 2 , Temperature 180℃, Water capacity 4.75
The test was conducted under test boiler conditions with a blowing water rate of 1.16/hr, and the amount of scale adhering to the inside of the test tube (SB-42 used, inner surface area 175 cm 2 ) was measured.
ボイラ給水として軟水を使用し、ボイラ水の水
質をPH11.0〜11.5（水酸化ナトリウム）、全シリ
カ濃度330〜390ppm、全亜鉛濃度14〜15ppm、
濃縮度13倍に設定して、スケール除去剤を添加せ
ずに45時間ボイラ運転したところ、62mgのスケー
ルがテストチユーブ内に付着していた。このスケ
ールを分析したところ、大半がZn4
（OH）2Si2O7・H2Oであつた。 Soft water is used as boiler water supply, and the boiler water quality is PH11.0 to 11.5 (sodium hydroxide), total silica concentration 330 to 390 ppm, total zinc concentration 14 to 15 ppm,
When the boiler was operated for 45 hours with the concentration set to 13 times without adding a scale remover, 62 mg of scale was found to have adhered to the inside of the test tube. When this scale was analyzed, the majority was Zn4
(OH) 2 Si 2 O 7・H 2 O.
つぎに、
アミノトリメチレンホスホン酸(a)
エチレンジアミンテトラメチルホスホン酸(b)
ヒドロキシエチリデンジホスホン酸(c)
１・２・４−トリカルボキシブタン−２−ホスホ
ン酸(d)
ニトリロトリ酢酸(e)
エチレンジアミンテトラ酢酸(f)
を、各々水系に140〜150ppm（亜鉛量の10倍）
添加して上記と同様の試験を行なつたところ、各
スケール付着量は次の通りとなつた。 Next, aminotrimethylenephosphonic acid (a) ethylenediaminetetramethylphosphonic acid (b) hydroxyethylidene diphosphonic acid (c) 1,2,4-tricarboxybutane-2-phosphonic acid (d) nitrilotriacetic acid (e) ethylenediaminetetra Add acetic acid (f) to the water system at 140 to 150 ppm (10 times the amount of zinc).
When the same test as above was carried out with the addition of these substances, the amount of each scale attached was as follows.
ａ ０mg ｂ ２mg
ｃ ０mg ｄ ７mg
ｅ ５mg ｆ ３mg
以上の結果から、本発明のスケール防止剤は極
めて優れたスケール防止効果を示すことが判明し
た。 a 0mg b 2mg c 0mg d 7mg e 5mg f 3mg From the above results, it was found that the scale inhibitor of the present invention exhibits an extremely excellent scale prevention effect.
Claims (1)
は異なつていてもよく、水素原子、炭素数１〜５
の低級アルキル基を表わし；Z1〜Z6は、各々、同
一もしくは異なつていてもよく、水素原子、アル
カリ金属原子、アンモニウムを表わす。） で示されるホスホン酸； 次式（）： ［式中、R1、R2及びR4は、各々、同一もしくは異
なつていてもよく、次の基(A)： （X1、Y1、Z1及びZ2は、前記（）式の場合と同
じ意味を有する。） を表わし；R3は、上記した基(A)、炭素数１〜５
の低級アルキル基を表わし；ｎは１〜３の整数を
表わす。］ で示されるホスホン酸； 次式（）： （式中、Ｘは水素原子、炭素数１〜５の低級アル
キル基を表わし；Ｙは水素原子、炭素数１〜５の
低級アルキル基、水酸基、アンモニウムを表わ
し；Z1〜Z4は前記（）式の場合と同じ意味を有
する。） で示されるホスホン酸； 次式（）： （式中、R1〜R6は、各々、同一もしくは異つてい
てもよく、水素原子、炭素数１〜５の低級アルキ
ル基、カルボキシル基を表わし；X1〜X3及び
Z1、Z2は前記（）式の場合と同じ意味を有す
る。） で示されるホスホン酸； 次式（）： （式中、X1、X2は各々同一もしくは異なつていて
もよく、Ｈ、−CH2−CH2−OHまたは−CH2−
COOZ2を表わし；Z1、Z2は前記（）式の場合
と同じ意味を有する。） で示されるα−アミノカルボン酸もしくは 次式（）： （式中、X1、X2、X3及びX4は、各々同一もしくは
異なつていてもよく、−CH2−CH2−OH、−CH2
−COOZ1を表わし、ｎは１〜３の整数を表わ
し、Z1は前記（）式の場合と同じ意味を有す
る。） で示されるα−アミノカルボン酸； 又はこれらの水溶性塩から選ばれる１種もしくは
２種以上の化合物から成る亜鉛びき鋼管又は亜鉛
を含む合金からなることを具備するボイラ水系用
スケール防止剤。 ２ 式（）で示されるホスホン酸がアミノトリ
メチルホスホン酸である特許請求の範囲第１項記
載のスケール防止剤。 ３ 式（）で示されるホスホン酸が２−ヒドロ
キシエチル−１・２−ジホスホン酸である特許請
求の範囲第１項記載のスケール防止剤。 ４ 式（）で示されるα−アミノカルボン酸が
エチレンジアミンテトラ酢酸である特許請求の範
囲第１項記載のスケール防止剤。 ５ 式（）で示されるα−アミノカルボン酸が
ニトリロトリ酢酸である特許請求の範囲第１項記
載のスケール防止剤。[Claims] Primary formula (): (In the formula, X 1 to X 3 and Y 1 to Y 3 may be the same or different, and each has a hydrogen atom, a carbon number of 1 to 5
represents a lower alkyl group; Z 1 to Z 6 may each be the same or different and represent a hydrogen atom, an alkali metal atom, or ammonium. ) Phosphonic acid represented by the following formula (): [In the formula, R 1 , R 2 and R 4 may each be the same or different, and the following group (A): (X 1 , Y 1 , Z 1 and Z 2 have the same meanings as in the above formula ()); R 3 is the group (A) described above, and has 1 to 5 carbon atoms.
represents a lower alkyl group; n represents an integer of 1 to 3; ] Phosphonic acid represented by the following formula (): (In the formula, X represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms; Y represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or ammonium; Z 1 to Z 4 are the above-mentioned ( ) Phosphonic acid represented by the following formula (): (In the formula, R 1 to R 6 may be the same or different, and each represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a carboxyl group ;
Z 1 and Z 2 have the same meanings as in the above formula (). ) Phosphonic acid represented by the following formula (): (In the formula, X 1 and X 2 may be the same or different, H, -CH 2 -CH 2 -OH or -CH 2 -
represents COOZ 2 ; Z 1 and Z 2 have the same meanings as in the above formula (). ) or α-aminocarboxylic acid represented by the following formula (): (In the formula, X 1 , X 2 , X 3 and X 4 may be the same or different, respectively, -CH 2 -CH 2 -OH, -CH 2
-COOZ 1 , n represents an integer of 1 to 3, and Z 1 has the same meaning as in the above formula (). ) A scale inhibitor for a boiler water system, comprising a galvanized steel pipe or an alloy containing zinc, comprising one or more compounds selected from α-aminocarboxylic acids represented by the following: or water-soluble salts thereof. 2. The scale inhibitor according to claim 1, wherein the phosphonic acid represented by formula () is aminotrimethylphosphonic acid. 3. The scale inhibitor according to claim 1, wherein the phosphonic acid represented by formula () is 2-hydroxyethyl-1,2-diphosphonic acid. 4. The scale inhibitor according to claim 1, wherein the α-aminocarboxylic acid represented by formula () is ethylenediaminetetraacetic acid. 5. The scale inhibitor according to claim 1, wherein the α-aminocarboxylic acid represented by formula () is nitrilotriacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57121349A JPS5912799A (en) | 1982-07-14 | 1982-07-14 | Antiscaling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57121349A JPS5912799A (en) | 1982-07-14 | 1982-07-14 | Antiscaling agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5912799A JPS5912799A (en) | 1984-01-23 |
| JPS6248560B2 true JPS6248560B2 (en) | 1987-10-14 |
Family
ID=14809072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57121349A Granted JPS5912799A (en) | 1982-07-14 | 1982-07-14 | Antiscaling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5912799A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171477A (en) * | 1991-05-31 | 1992-12-15 | W. R. Grace & Co.-Conn. | Corrosion inhibition in chelant solutions |
| WO2007080811A1 (en) * | 2006-01-11 | 2007-07-19 | Kurita Water Industries Ltd. | Antiscaling agent and antiscaling method |
| JP5577571B2 (en) * | 2008-03-31 | 2014-08-27 | 栗田工業株式会社 | Scale inhibitor for circulating cooling water system in steel manufacturing process, and scale prevention method |
| JP2015112557A (en) * | 2013-12-12 | 2015-06-22 | 中部キレスト株式会社 | Deposition suppressor |
| JP6357817B2 (en) * | 2014-03-14 | 2018-07-18 | 栗田工業株式会社 | Method for preventing zinc-based scale and zinc-based scale inhibitor |
| CN107902771A (en) * | 2017-10-24 | 2018-04-13 | 陈木玲 | A kind of reverse osmosis dirt dispersion agent and its preparation process |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666664A (en) * | 1971-05-12 | 1972-05-30 | Nalco Chemical Co | Compositions and methods for controlling scale |
| JPS4839348A (en) * | 1971-09-23 | 1973-06-09 | ||
| JPS4949887A (en) * | 1972-05-26 | 1974-05-15 | ||
| JPS528663A (en) * | 1975-07-10 | 1977-01-22 | Sakae Katayama | Treatment of waste water used for dust collection from waste gas |
| GB1473488A (en) * | 1976-01-15 | 1977-05-11 | Calgon Corp | Sludge prevention and removal |
| JPS5387051A (en) * | 1976-12-28 | 1978-08-01 | Kurita Water Ind Ltd | Prevention against corrosion and scaling in heat exchanger or its pipes |
| US4255259A (en) * | 1979-09-18 | 1981-03-10 | Chemed Corporation | Scale inhibition |
-
1982
- 1982-07-14 JP JP57121349A patent/JPS5912799A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666664A (en) * | 1971-05-12 | 1972-05-30 | Nalco Chemical Co | Compositions and methods for controlling scale |
| JPS4839348A (en) * | 1971-09-23 | 1973-06-09 | ||
| JPS4949887A (en) * | 1972-05-26 | 1974-05-15 | ||
| JPS528663A (en) * | 1975-07-10 | 1977-01-22 | Sakae Katayama | Treatment of waste water used for dust collection from waste gas |
| GB1473488A (en) * | 1976-01-15 | 1977-05-11 | Calgon Corp | Sludge prevention and removal |
| JPS5387051A (en) * | 1976-12-28 | 1978-08-01 | Kurita Water Ind Ltd | Prevention against corrosion and scaling in heat exchanger or its pipes |
| US4255259A (en) * | 1979-09-18 | 1981-03-10 | Chemed Corporation | Scale inhibition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5912799A (en) | 1984-01-23 |
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