JPS6348953B2 - - Google Patents
Info
- Publication number
- JPS6348953B2 JPS6348953B2 JP57208417A JP20841782A JPS6348953B2 JP S6348953 B2 JPS6348953 B2 JP S6348953B2 JP 57208417 A JP57208417 A JP 57208417A JP 20841782 A JP20841782 A JP 20841782A JP S6348953 B2 JPS6348953 B2 JP S6348953B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- acid
- corrosion inhibitor
- total
- 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
- 230000007797 corrosion Effects 0.000 claims description 34
- 238000005260 corrosion Methods 0.000 claims description 34
- 239000003112 inhibitor Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 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 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- -1 iron and aluminum Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 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 1
- 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
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 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 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- AJEDYPTWOHVJRW-UHFFFAOYSA-N NC(CP(O)(O)=O)P(=O)(OC)OC Chemical compound NC(CP(O)(O)=O)P(=O)(OC)OC AJEDYPTWOHVJRW-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、金属の腐食防止剤に関し、更に詳し
くは、水中、特に、淡水中における金属材料の腐
食防止剤に関するものである。
主として淡水中、例えば、開放循環式冷却水系
などにおける鉄やアルミニウム等の金属の腐食を
防止するためには、従来はクロム酸塩を主剤とす
る腐食防止剤が使用されてきた。クロム酸塩系の
腐食防止剤は優れた防食効果を有するが、その強
い酸化力等に基く毒性が強いという欠点をも有す
るため、クロム含有廃水の排出が厳しく規制され
ている。
それ故に、近年、水系で使用される金属の腐食
防止剤としては、毒性のほとんどない正リン酸
塩、重合リン酸塩、ホスホン酸塩などの各種のリ
ン酸系化合物を主剤とするものが主流となつてき
ている。これらの各種のリン酸系化合物を主剤と
する腐食防止剤は、良好な防食効果を得るには、
全リン酸根換算濃度（以下「Ｔ−PO4濃度」とい
う。）が5ppm以上であることが必要であり、通常
は10ppm以上になるように水中に添加されてい
る。これらのリン酸系化合物は毒性がほとんどな
い反面、微生物の栄養源となり、その生育を促進
して、いわゆる水域の富栄養化と関連して発生す
る赤潮などの障害の一つの原因物質となつてい
る。従つて、富栄養化防止対策の一つとして、リ
ンの閉鎖水域への排出量を極力減少させることが
必要であり、リンの排出規制が実施されつつあ
る。
本発明は、このようなリンの排出規制に対応し
ようとするものであり、3ppm以下のＴ−PO4濃
度においても優れた防食効果を発揮できる金属の
腐食防止剤を提供することを目的とする。
本発明者は、前記した点に鑑みて鋭意研究を重
ねた結果、前記腐食防止剤として、ホスホン酸、
及び水溶性アルミン酸塩若しくは水溶性アルミニ
ウム塩、、並びにアクリル酸系、メタクリル酸系
若しくはマレイン酸系水溶性ポリマーからなる組
成物を用いることにより、本発明の目的を達成で
きることを見出し、本発明を完成するに至つた。
即ち、本発明の金属の腐食防止剤は、
(a) ホスホン酸又はその水溶性塩、
(b) 水溶性アルミン酸塩又は水溶性アルミニウム
塩
並びに
(c) アクリル酸系水溶性ポリマー、メタクリル酸
系水溶性ポリマー及びマレイン酸系水溶性ポリ
マーからなる群より選ばれる少なくとも一種の
水溶性ポリマーを含有することを特徴とするも
のである。
以下、本発明を更に詳細に説明する。
本発明の第１の組成分（(a)成分）をなすホスホ
ン酸又はその水溶性としては、下記の如き式
（）、（）、（）、（）で示される化合物又は
塩が例示される。
式（）：
（式中、X1〜X3及びY1〜Y3は、各々、同一又は
異なつていてもよく、水素原子又は炭素数１〜５
の低級アルキル基を表わし；Z1〜Z6は、各々、同
一又は異なつていてもよく、水素原子、アルカリ
金属原子又はアンモニウム基を表わす。）
上記（）式で表わされるホスホン酸又はその
水溶性塩としては、次のものが例示される。
() アミノトリメチルホスホン酸（以下
「AMP」という。）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ノ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（）：
〔式中、R1、R2及びR4は、各々、同一又は異な
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)又は炭素数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。〕
上記（）式で表わされるホスホン酸又はその
水溶性塩としては、次のものが例示される。
(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（）：
（式中、Ｘは水素原子又は炭素数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、水酸基又はアンモニウム基を
表わし；Z1〜Z4は前記（）式の場合と同じ意味
を有する。）
上記（）式で表わされるホスホン酸又はその
水溶性塩としては、次のものが例示される。
(1) ヒドロキシエチリデンジホスホン酸（以下
「HEDP」という。）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（）：
（式中、R1〜R6は、各々、同一又は異なつてい
てもよく、水素原子、炭素数１〜５の低級アルキ
ル基又は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。）
上記（）式で表わされるホスホン酸又はその
水溶性塩としては、次のものが例示できる。
(1) １，２，４−トリカルボキシブタン−２−ホ
スホン酸（以下「TCBP」という。）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
本発明の第２の組成分（(b)成分）をなす水溶性
アルミン酸塩としては、アルミン酸ナトリウム、
アルミン酸カリウムなどが；水溶性アルミニウム
塩としては、塩化アルミニウム、ポリ塩化アルミ
ニウム、硫酸アルミニウム、硝酸アルミニウム、
酢酸アルミニウムなどが挙げられる。
本発明の第３の組成分（(c)成分）をなす水溶性
ポリマーとしては、ポリアクリル酸、ポリメタク
リル酸、ポリマレイン酸、及びアクリル酸、メタ
クリル酸又はマレイン酸の二成分系共重合体、三
成分系共重合体などの共重合体、並びにこれらの
塩が挙げられる。
アクリル酸、メタクリル酸又はマレイン酸と共
重合させる単量体としては、これらの３種の単量
体の他に代表的なものとして、フマル酸、イタコ
ン酸、アクリルアミド、アクリル酸エステル、酢
酸ビニル、スチレン、エチレンオキサイド、アク
リル酸ヒドロキシアルキルエステル、アクリロニ
トリル、エチレン、ｎ−ブチレン、イソブチレ
ン、アリルスルホン酸、ビニルスルホン酸、スチ
リルスルホン酸などが挙げられる。
これらの単量体の１種あるいは２種以上を共重
合して得られる水溶性ポリマーは、その分子量が
500〜100000であるものが好ましく、1000〜20000
であるものが更に好ましい。また、これらの塩と
しては、ナトリウム塩、カリウム塩、アンモニウ
ム塩などが挙げられる。
本発明において、(a)成分と(b)成分との配合比
は、防食効果を考慮すると、(a)成分の全リン酸根
換算量（以下「Ｔ−PO4量」という。）と(b)成分
の全アルミニウム金属換算量（以下「Ｔ−Al量」
という。）との重量比が、１〜10：10〜１である
ことが好ましく、２〜１：１〜４であることが更
に好ましい。
また、(a)成分＋(b)成分と(c)成分との配合比は、
(a)成分のＴ−PO4量と(b)成分のＴ−Al量との合計
量と、(c)成分の全実質重量との重量比が５〜１：
１〜10であることが好ましく、２〜１：１〜５で
あることが更に好ましい。
本発明の腐食防止剤の使用に際しては、予め、
各成分を所定の配合比になるように配合し、一液
化しておいてもよいし、使用時に直接、各成分を
対象水系に所定の添加割合になるように添加して
もよい。本発明の腐食防止剤の使用濃度は、前述
した各成分の配合比の範囲内において、Ｔ−PO4
濃度が0.5ppm以上で、全アルミニウム金属換算
濃度（以下「Ｔ−Al濃度」という。）が0.5ppm以
上で水溶性ポリマーの全実質濃度が0.2ppm以上
であることが好ましい。一般に、静置状態の水中
では添加量が大であることが好ましく、流動状態
の水中では少量の添加でも良好な防食効果が得ら
れる。また、本発明の金属の腐食防止剤は、使用
初期に高濃度の添加を行なうと、その後、使用濃
度を低下させても良好な防食効果が得られる。
更に、本発明の金属の腐食防止剤は使用に際し
て被処理水系のPHを特に調整する必要はなく、弱
酸性からアルカリ性の広いPH範囲の水中で良好な
防食効果が得られる。
本発明の金属の腐食防止剤が使用されるのは、
一般の冷却水系の他、水又は水溶液による鉄材そ
の他の金属の腐食が問題となる場合で、例えば、
休止中のボイラの保管、タンク類の水圧試験時な
どの金属の腐食防止に有効である。更に、本発明
の金属の腐食防止剤は、スケール防止効果と汚れ
防止効果をも有している。
当然ながら、この金属の腐食防止剤は使用濃度
において無色透明で、かつ、実質的に無毒で取扱
い上の危険もない。
更に、本発明の金属の腐食防止剤は、従来のリ
ン酸系の腐食防止剤に比し、低いＴ−PO4濃度に
おいても有効に作用するため、赤潮などの障害が
生じる危険性が少ないという長所をも有する。
また、本発明の金属の腐食防止剤は、既存の金
属の腐食防止剤、例えば、クロム酸塩類、正リン
酸塩類、重合リン酸塩類、亜鉛塩類、亜硝酸塩
類、ケイ酸塩類、オキシカルボン酸塩類、アミン
類、トリアゾール類、メルカプトベンゾチアゾー
ル類、イミダゾリン類などと適宜併用することも
可能である。
以下、実施例及び比較例により本発明を更に詳
細に説明する。
実施例１〜13及び比較例１〜12
本発明の金属の腐食防止剤を、PH8.3、カルシ
ウム硬度150ppm（CaCO3換算量）、Ｍ−アルカリ
度150ppm（CaCO3換算量）、塩素イオン濃度
200ppm、硫酸イオン濃度200ppmの試験水に添加
し、水温を30℃に保つた。この試験水中で軟鋼の
試験片を160rpmで５日間回転させ、試験前後の
試験片の重量差（腐食減量）を求め、これより腐
食速度（mg／ｄm2・day）を算出し、金属の腐食
防止剤の効果を判定した。また、各配合成分を単
独に用いた場合、２成分を併用した場合及び腐食
防止剤を添加しなかつた場合についても同様の実
験を行なつた。その結果を表に示す。
表に示した試験結果より、本発明の腐食防止剤
は３種の有効成分を使用することによつて、相乗
的に優れた防食効果を有することが判る。
The present invention relates to a corrosion inhibitor for metals, and more particularly to a corrosion inhibitor for metal materials in water, particularly fresh water. In order to prevent corrosion of metals such as iron and aluminum, mainly in fresh water, for example, in open circulation cooling water systems, corrosion inhibitors based on chromate have conventionally been used. Although chromate-based corrosion inhibitors have excellent anticorrosion effects, they also have the disadvantage of being highly toxic due to their strong oxidizing power, and therefore, the discharge of chromium-containing wastewater is strictly regulated. Therefore, in recent years, the mainstream of metal corrosion inhibitors used in aqueous systems are those based on various phosphoric acid compounds such as orthophosphates, polymerized phosphates, and phosphonates, which have almost no toxicity. It's becoming more and more common. Corrosion inhibitors based on these various phosphoric acid compounds must be used in order to obtain good corrosion protection effects.
It is necessary that the total phosphate concentration (hereinafter referred to as "T-PO 4 concentration") is 5 ppm or more, and it is usually added to water so that it is 10 ppm or more. Although these phosphoric acid compounds have almost no toxicity, they serve as nutritional sources for microorganisms, promoting their growth and becoming one of the causative substances of disorders such as red tide that occur in connection with the eutrophication of water bodies. There is. Therefore, as one measure to prevent eutrophication, it is necessary to reduce the amount of phosphorus discharged into closed water bodies as much as possible, and phosphorus discharge regulations are being implemented. The present invention is intended to comply with such phosphorus emission regulations, and aims to provide a metal corrosion inhibitor that can exhibit excellent corrosion prevention effects even at T-PO 4 concentrations of 3 ppm or less. . As a result of extensive research in view of the above points, the present inventors have discovered that phosphonic acid,
It has been discovered that the objects of the present invention can be achieved by using a composition comprising a water-soluble aluminate or a water-soluble aluminum salt, and an acrylic acid-based, methacrylic acid-based, or maleic acid-based water-soluble polymer. It was completed. That is, the metal corrosion inhibitor of the present invention comprises (a) phosphonic acid or a water-soluble salt thereof, (b) a water-soluble aluminate or a water-soluble aluminum salt, and (c) an acrylic acid-based water-soluble polymer or a methacrylic acid-based water-soluble polymer. It is characterized by containing at least one water-soluble polymer selected from the group consisting of water-soluble polymers and maleic acid-based water-soluble polymers. The present invention will be explained in more detail below. Examples of the phosphonic acid or water-soluble phosphonic acid constituting the first component (component (a)) of the present invention include compounds or salts represented by the following formulas (), (), (), and (). . formula(): (In the formula, X 1 to X 3 and Y 1 to Y 3 may each be the same or different, and each has a hydrogen atom or a carbon number of 1 to 5
represents a lower alkyl group; each of Z 1 to Z 6 may be the same or different and represents a hydrogen atom, an alkali metal atom or an ammonium group. ) The following are exemplified as the phosphonic acid or its water-soluble salt represented by the above formula (). () Aminotrimethylphosphonic acid (hereinafter referred to as "AMP") and its sodium, potassium, and ammonium salts (2) Aminodimethylphosphonomonoethylphosphonic acid and its sodium, potassium, and ammonium salts 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 or has 1 to 1 carbon atoms.
5 represents a lower alkyl group; n represents an integer of 1 to 3; ] The following are exemplified as the phosphonic acid or its water-soluble salt represented by the above formula (). (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 ( ): (In the formula, X represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms; Y is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.
represents a lower alkyl group, hydroxyl group or ammonium group; Z1 to Z4 have the same meanings as in the above formula (). ) The following are exemplified as the phosphonic acid or its water-soluble salt represented by the above formula (). (1) Hydroxyethylidene diphosphonic acid (hereinafter referred to as "HEDP") and its sodium, potassium, and ammonium salts (2) Hydroxypropylidene diphosphonic acid and its sodium, potassium, and ammonium salts Formula (): (In the formula, R 1 to R 6 may be the same or different, and represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a carboxyl group; X 1 to X 3 and
Z 1 and Z 2 have the same meanings as in the above formula (). ) Examples of the phosphonic acid or water-soluble salt thereof represented by the above formula () include the following. (1) 1,2,4-tricarboxybutane-2-phosphonic acid (hereinafter referred to as "TCBP") and its sodium, potassium, and ammonium salts (2) 1,2-dicarboxybutane-2-phosphonic acid and its sodium, potassium, and ammonium salts Sodium, potassium, ammonium salt (3) 1,2,4-tricarboxyhexane-2-
Phosphonic acid and its sodium, potassium, ammonium salts The water-soluble aluminates constituting the second component (component (b)) of the present invention include sodium aluminate,
Potassium aluminate, etc.; water-soluble aluminum salts include aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum nitrate,
Examples include aluminum acetate. The water-soluble polymer constituting the third component (component (c)) of the present invention includes polyacrylic acid, polymethacrylic acid, polymaleic acid, and a binary copolymer of acrylic acid, methacrylic acid, or maleic acid, Examples include copolymers such as ternary copolymers, and salts thereof. In addition to these three types of monomers, typical monomers to be copolymerized with acrylic acid, methacrylic acid, or maleic acid include fumaric acid, itaconic acid, acrylamide, acrylic ester, vinyl acetate, Examples include styrene, ethylene oxide, hydroxyalkyl acrylate, acrylonitrile, ethylene, n-butylene, isobutylene, allylsulfonic acid, vinylsulfonic acid, and styrylsulfonic acid. The water-soluble polymer obtained by copolymerizing one or more of these monomers has a molecular weight of
Preferably 500-100000, 1000-20000
It is more preferable that Further, examples of these salts include sodium salts, potassium salts, ammonium salts, and the like. In the present invention, the blending ratio of component (a) and component (b) is determined based on the amount of total phosphate radical equivalent of component (a) (hereinafter referred to as "T- PO4 amount") and (b), considering the anticorrosion effect. ) component in terms of total aluminum metal (hereinafter referred to as “T-Al amount”)
That's what it means. ) is preferably 1-10:10-1, more preferably 2-1:1-4. In addition, the blending ratio of component (a) + component (b) and component (c) is:
The weight ratio of the total amount of T-PO 4 of component (a) and T-Al of component (b) to the total real weight of component (c) is 5 to 1:
The ratio is preferably 1 to 10, and more preferably 2 to 1:1 to 5. When using the corrosion inhibitor of the present invention, in advance,
Each component may be blended at a predetermined mixing ratio and made into one liquid, or each component may be directly added to the target aqueous system at a predetermined addition ratio at the time of use. The concentration of the corrosion inhibitor of the present invention used is T-PO 4 within the range of the mixing ratio of each component described above.
It is preferable that the concentration is 0.5 ppm or more, the total aluminum metal equivalent concentration (hereinafter referred to as "T-Al concentration") is 0.5 ppm or more, and the total substantial concentration of the water-soluble polymer is 0.2 ppm or more. Generally, it is preferable to add a large amount in water in a stationary state, and a good anticorrosive effect can be obtained even in a small amount in water in a fluid state. Further, when the metal corrosion inhibitor of the present invention is added at a high concentration at the beginning of use, a good corrosion prevention effect can be obtained even if the concentration is lowered thereafter. Furthermore, when using the metal corrosion inhibitor of the present invention, there is no need to particularly adjust the pH of the water system to be treated, and a good corrosion prevention effect can be obtained in water with a wide pH range from weakly acidic to alkaline. The metal corrosion inhibitor of the present invention is used for:
In addition to general cooling water systems, in cases where corrosion of iron materials and other metals by water or aqueous solutions is a problem, for example,
Effective for preventing corrosion of metals during storage of idle boilers and water pressure tests of tanks. Furthermore, the metal corrosion inhibitor of the present invention also has a scale-preventing effect and a stain-preventing effect. Naturally, this metal corrosion inhibitor is colorless and transparent at the concentrations used, and is substantially non-toxic and poses no hazard in handling. Furthermore, the metal corrosion inhibitor of the present invention works more effectively even at low T-PO 4 concentrations than conventional phosphoric acid-based corrosion inhibitors, so there is less risk of causing problems such as red tide. It also has advantages. In addition, the metal corrosion inhibitor of the present invention can be applied to existing metal corrosion inhibitors such as chromates, orthophosphates, polymerized phosphates, zinc salts, nitrites, silicates, and oxycarboxylic acids. It is also possible to use it in combination with salts, amines, triazoles, mercaptobenzothiazoles, imidazolines, etc. as appropriate. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Examples 1 to 13 and Comparative Examples 1 to 12 The metal corrosion inhibitor of the present invention was used at pH 8.3, calcium hardness 150 ppm (CaCO 3 equivalent amount), M-alkalinity 150 ppm (CaCO 3 equivalent amount), and chloride ion concentration.
It was added to test water with a sulfate ion concentration of 200 ppm and the water temperature was maintained at 30°C. A mild steel test piece was rotated in this test water at 160 rpm for 5 days, and the weight difference (corrosion loss) between the test piece before and after the test was determined. From this, the corrosion rate (mg/dm 2・day) was calculated, and the corrosion rate of the metal was calculated. The effectiveness of the inhibitor was determined. In addition, similar experiments were conducted in cases where each compounded component was used alone, when two components were used in combination, and when no corrosion inhibitor was added. The results are shown in the table. From the test results shown in the table, it can be seen that the corrosion inhibitor of the present invention has a synergistically excellent anticorrosive effect by using three types of active ingredients.
【表】【table】
Claims (1)
塩並びに (c) アクリル酸系水溶性ポリマー、メタクリル酸
系水溶性ポリマー及びマレイン酸系水溶性ポリ
マーからなる群より選ばれる少なくとも一種の
水溶性ポリマーを含有することを特徴とする金
属の腐食防止剤。 ２ ホスホン酸又はその水溶性塩が二種以上の混
合物である特許請求の範囲第１項記載の金属の腐
食防止剤。 ３ 水溶性アルミン酸塩又は水溶性アルミニウム
塩が二種以上の混合物である特許請求の範囲第１
項又は第２項記載の金属の腐食防止剤。 ４ ホスホン酸又はその水溶性塩の全リン酸根換
算量と、水溶性アルミン酸塩又は水溶性アルミニ
ウム塩の全アルミニウム金属換算量との重量比が
１〜10：10〜１である特許請求の範囲第１項ない
し第３項のいずれかに記載の金属の腐食防止剤。 ５ ホスホン酸又はその水溶性塩の全リン酸根換
算量と水溶性アルミン酸塩又は水溶性アルミニウ
ム塩の全アルミニウム金属換算量との合計量と、
前記水溶性ポリマーの全実質重量との重量比が５
〜１：１〜10である特許請求の範囲第１項ないし
第４項のいずれかに記載の金属の腐食防止剤。[Scope of Claims] 1 (a) Phosphonic acid or a water-soluble salt thereof, (b) Water-soluble aluminate or water-soluble aluminum salt, and (c) Water-soluble acrylic acid polymer, water-soluble methacrylic acid polymer, and malein. A metal corrosion inhibitor characterized by containing at least one water-soluble polymer selected from the group consisting of acid-based water-soluble polymers. 2. The metal corrosion inhibitor according to claim 1, which is a mixture of two or more phosphonic acids or water-soluble salts thereof. 3 Claim 1 in which the water-soluble aluminate or water-soluble aluminum salt is a mixture of two or more types.
Corrosion inhibitor for metals according to item 1 or 2. 4 Claims in which the weight ratio of the amount of phosphonic acid or its water-soluble salt in terms of total phosphate radicals to the amount of water-soluble aluminate or water-soluble aluminum salt in terms of total aluminum metal is 1 to 10:10 to 1. The metal corrosion inhibitor according to any one of items 1 to 3. 5. The total amount of phosphonic acid or its water-soluble salt in terms of total phosphate radicals and the amount of water-soluble aluminate or water-soluble aluminum salt in terms of total aluminum metal,
The weight ratio to the total real weight of the water-soluble polymer is 5.
The metal corrosion inhibitor according to any one of claims 1 to 4, wherein the ratio is 1 to 1:1 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20841782A JPS59100272A (en) | 1982-11-30 | 1982-11-30 | Corrosion preventive agent for metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20841782A JPS59100272A (en) | 1982-11-30 | 1982-11-30 | Corrosion preventive agent for metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59100272A JPS59100272A (en) | 1984-06-09 |
| JPS6348953B2 true JPS6348953B2 (en) | 1988-10-03 |
Family
ID=16555884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20841782A Granted JPS59100272A (en) | 1982-11-30 | 1982-11-30 | Corrosion preventive agent for metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59100272A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0751758B2 (en) * | 1986-05-23 | 1995-06-05 | 株式会社片山化学工業研究所 | Metal anticorrosive |
| US4873280A (en) * | 1986-11-06 | 1989-10-10 | Nalco Chemical Company | Water clarification process and composition and method |
| US4734274A (en) * | 1986-11-06 | 1988-03-29 | Nalco Chemical Company | Stabilization of aqueous alkali metal aluminate solutions |
| US4917803A (en) * | 1989-03-02 | 1990-04-17 | Nalco Chemical Company | Water clarification process |
| EP0822270A1 (en) | 1996-07-30 | 1998-02-04 | Solutia Europe N.V./S.A. | Water-treatment composition and method of use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50110949A (en) * | 1973-10-09 | 1975-09-01 |
-
1982
- 1982-11-30 JP JP20841782A patent/JPS59100272A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50110949A (en) * | 1973-10-09 | 1975-09-01 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59100272A (en) | 1984-06-09 |
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