JPS6247434B2 - - Google Patents
Info
- Publication number
- JPS6247434B2 JPS6247434B2 JP57215389A JP21538982A JPS6247434B2 JP S6247434 B2 JPS6247434 B2 JP S6247434B2 JP 57215389 A JP57215389 A JP 57215389A JP 21538982 A JP21538982 A JP 21538982A JP S6247434 B2 JPS6247434 B2 JP S6247434B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- water treatment
- treatment agent
- salts
- structural unit
- 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 62
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- -1 alkylamine salts Chemical class 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000013535 sea water Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000012851 eutrophication Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 description 1
- 229960001171 acetohydroxamic acid Drugs 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 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
- 235000021049 nutrient content Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 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
- 239000002455 scale inhibitor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 150000003681 vanadium 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
- 150000003751 zinc Chemical class 0.000 description 1
Description
本発明は、水処理剤に関し、更に詳しくは、水
系における金属の腐食やスケールの生成を防止す
ることができる水処理剤に関する。
一般に、石油精製プラント、化学工業プラン
ト、空調プラント等の冷却水系及びボイラー水系
においては、金属管表面や水路壁面、ボイラーの
伝熱面等に、腐食やスケールが生成し、効率低下
を招くだけでなく、閉塞事故をもひきおこしかね
ず、常に腐食やスケールの生成を防止するように
細心の注意が払われている。
従来、このような水系に対し、例えばスケール
を防止するためにポリアクリル酸塩に代表される
合成重合体が適用され、一定の成果が得られてい
る。
しかし、従来の合成重合体は全ての水系に対し
て等しくスケール防止効果を発揮できる訳にはい
かず、例えば、カルシウム硬度が250ppm
（CaCO3換算量）以上の高カルシウム硬度水系に
前記のポリアクリル酸塩を添加しても、水中のカ
ルシウムイオンとポリアクリル酸塩とが反応して
不溶性塩を形成してしまい、スケール抑制能を発
揮できないばかりか、むしろスケールの原因にす
らなることがあつた。
一方、前記の水系における金属の腐食防止のた
めには、クロム酸塩やリン酸塩が用いられてき
た。
しかし、クロム酸塩は、その毒性のために排出
規制の対象となつている。また、リン酸塩につい
ても閉鎖水域における富栄養化の原因となるため
規制の動向が顕著になりつつある。
また、クエン酸、酒石酸等のオキシカルボン酸
類や安息香酸類等の有機化合物も適用されている
が、これらの有機化合物は微生物により容易に分
解されるばかりでなく、系外に排出されると
COD源となるため、使用が敬遠される傾向にあ
る。
本発明は、このような従来技術の有する欠点を
解決するために鋭意研究した結果完成されたもの
であつて、全ての水系に対して有効にスケール防
止効果又は防食効果を発揮でき、かつ、毒性が低
く、閉鎖水域における富栄養化の原因となること
がない水処理剤を提供することを目的とする。
即ち、本発明の水処理剤は、
次式：
（式中、R1は水素原子又はメチル基を表わ
し、X1は水素原子、一価若しくは二価の金属原
子、アンモニウム基又は有機アミン基を表わし、
ｍは金属原子の価数又は１を表わす。）
で示される構造単位(A)と、
次式：
（式中、R2は水素原子又はメチル基を表わ
し、X2は水素原子、一価若しくは二価の金属原
子、アンモニウム基又は有機アミン基を表わし、
ｎは金属原子の価数又は１を表わす。）
で示される構造単位(B)とを有する分子量500〜
50000の水溶性共重合体であつて、かつ、構造単
位(A)の共重合体全体に占める割合が0.1〜2.5モル
％であることを特徴とするものである。
本発明の水処理剤は、従来の公知の方法によつ
て得ることができる。
例えば、構造単位(A)を形成する次式（）：
（式中、R1、X1及びｍは前記と同義である。）
で示される化合物及び構造単位(B)を形成する次式
（）：
（式中、R2、X2及びｎは前記と同義である。）
で示される化合物並びに必要に応じて任意の単量
体を所望のモル比で水に加え、過酸化物等の重合
開始剤を添加し、加熱することにより、対応する
モル比の構造単位からなる水溶性共重合体、即ち
本発明の水処理剤を得ることができる。
本発明に用いられる前記式（）で示される化
合物としては、アリルスルホン酸及びメタリルス
ルホン酸並びにそれらのナトリウム塩、カリウム
塩、リチウム塩、アンモニウム塩及びトリエタノ
ールアミン塩、アルキルアミン塩等の有機アミン
塩等が挙げられる。
前記式（）で示される化合物としては、アク
リル酸及びメタクリル酸並びにそれらのナトリウ
ム塩、カリウム塩、リチウム塩、アンモニウム塩
及びトリエタノールアミン塩、、アルキルアミン
塩等の有機アミン塩等が挙げられる。
本発明の水処理剤は、構造単位(A)及び(B)の他
に、必要に応じて他の構造単位(C)も用いられる。
構造単位(A)及び(B)以外の構造単位(C)を形成する単
量体としては、例えば、イタコン酸、フマル酸、
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、ビ
ニルスルホン酸、スチリルスルホン酸等が挙げら
れる。構造単位(C)は一種に限られず、二種以上で
もよい。
本発明の共重合体は、その効果を考慮すると、
分子量500〜50000であることが必要であり、特に
分子量500〜10000であることが好ましい。同様
に、構造単位(A)の共重合体全体に占める割合は
0.1〜2.5モル％であることが必要であり、特に、
0.1モル％以上1.0モル％未満であることが好まし
い。
本発明において、構造単位(A)及び(B)以外の構造
単位(C)を形成せしめる場合には、該構造単位(C)の
共重合体全体に占める割合は、一般には、0.1〜
10モル％であり、特に0.1〜2.5モル％であること
が好ましい。
本発明の水処理剤は、前記共重合体を有効成分
とするものであり、従来の水処理剤と同様に対象
水系に連続的または間欠的に直接添加して使用す
る。本発明の水処理剤は、純水、軟水、水道水及
び工業用水等あらゆる水質に適応でき、使用濃度
は、目的に応じて決定されるものであるが、一般
には有効成分として0.1〜500ppmであり、特に
0.5〜200ppmであることが好ましい。また、対象
水系のPH範囲は特に制限はないが、一般にPH６〜
14であり、好ましくはPH６〜12である。
対象水系の具体例としては、ボイラー水系や開
放、又は密閉循環式冷却水系、一過式冷却水系、
ブライン水系、一部の転炉集塵水系、高炉転炉等
のドライピツトの冷却水系、コークス工場等にお
けるアンモニア蒸留塔水系、都市ゴミ清掃工場等
の焼却灰水系、海水脱塩装置等が挙げられる。ま
た、近年循環冷却水系において、高カルシウム硬
度水系となるような高濃縮運転が行なわれること
が多いが、このような高濃縮運転は本発明の水処
理剤にとつて、むしろ特有のスケール防止効果が
得られる条件となるので好ましい。
一方、逆に、特に純水や軟水を用いる冷却水系
では、溶存塩類が少なく、このことが本願発明の
水処理剤にとつてむしろ特有の防食効果が得ら
れ、従来の水処理剤と比べると優れた腐食抑制効
果を発揮して好ましい。
本発明の水処理剤は、単独で用いても鉄鋼等を
材質とする水系に対して充分効果があるが、他の
金属も併用されている場合などにおいては、必要
により他の水処理剤、例えば、オキシカルボン酸
類；メルカプトベンゾチアゾール等のチアゾール
類；ベンゾトリアゾール等のアゾール類；ヒドラ
ジン類、シクロヘキシルアミン、アルキルアミ
ン、アルカノールアミン、ポリアミン等の水溶性
アミン類；エチレンイミン、ピロリジン、ピペリ
ジン、ピペラジン、ケチミン等のイミン類；ホル
ムヒドロキサム酸、アセトヒドロキサム酸、ベン
ズヒドロキシサム酸等のヒドロキサム酸類；オレ
イン酸等の長鎖脂肪族カルボン酸類；安息香酸、
フタル酸等の芳香族カルボン酸類；カテコール
類；タンニン類；リグニン類；ホスホン酸類；等
の有機化合物や亜硝酸塩、ケイ酸塩、各種リン酸
塩、ホウ酸塩、亜鉛塩、ニツケル塩、モリブデン
塩、アルミニウム塩、アルミン酸塩、タングステ
ン塩、バナジウム塩等の無機塩類などを併用して
もよい。
また、必要に応じ、他の公知のスケール防止剤
やスライムコントロール剤を併用してもよい。
本発明の水処理剤は、従来の水処理剤では効果
的にスケール生成を抑制することができなかつた
ような高カルシウム硬度の水系に対しても、効果
的にスケール生成を抑制することができる。
更に、本発明の水処理剤は、毒性が低く、か
つ、富栄養化の原因とならないばかりか、微生物
により容易に分解されることがないので、BOD
源となることがないという長所をも有する。
以下、実施例により本発明を更に詳細に説明す
るが、本発明はこれらの実施例に限定されるもの
ではない。
実施例 １
脱塩水にCaCl2・2H2O 300ppm（CaCO3換算
量）とNaHCO3 300ppm（CaCO3換算量）を添加
し、PHを9.1に調整した試験液500mlを三角フラス
コに入れ、更に第１表記載の水処理剤（但し、い
ずれもナトリウム塩）20ppmを添加し、密栓し
た後、水温50℃の恒温水槽中に浸漬し、20時間静
置した。次に、この試験液を0.1μのメンブレン
フイルターで過し、液中のカルシウムイオン
濃度をEDTA法により測定した。結果を第１表に
示す。
The present invention relates to a water treatment agent, and more particularly to a water treatment agent that can prevent metal corrosion and scale formation in an aqueous system. In general, in the cooling water systems and boiler water systems of oil refinery plants, chemical industry plants, air conditioning plants, etc., corrosion and scale form on the metal pipe surfaces, waterway walls, boiler heat transfer surfaces, etc., which only leads to a decrease in efficiency. Extreme care must always be taken to prevent corrosion and scale formation, as this can lead to blockage accidents. Conventionally, synthetic polymers typified by polyacrylates have been applied to such aqueous systems to prevent scale, for example, and certain results have been obtained. However, conventional synthetic polymers cannot exhibit the same scale prevention effect in all water systems; for example, when the calcium hardness is 250 ppm,
Even if the above-mentioned polyacrylate is added to a water system with a high calcium hardness of (CaCO 3 equivalent amount) or more, the calcium ions in the water and the polyacrylate will react to form an insoluble salt, which will reduce the scale control ability. Not only could this not be achieved, but it could even be the cause of scale. On the other hand, chromates and phosphates have been used to prevent corrosion of metals in aqueous systems. However, chromate is subject to emission regulations due to its toxicity. Additionally, there is a growing trend towards regulation of phosphates as they cause eutrophication in closed water bodies. In addition, organic compounds such as oxycarboxylic acids such as citric acid and tartaric acid and benzoic acids are also used, but these organic compounds are not only easily decomposed by microorganisms, but also can be easily discharged from the system.
Because it is a source of COD, its use tends to be avoided. The present invention was completed as a result of intensive research to solve the drawbacks of the prior art, and is capable of effectively exhibiting scale prevention or corrosion prevention effects in all aqueous systems, and is non-toxic. The purpose of the present invention is to provide a water treatment agent that has a low nutrient content and does not cause eutrophication in closed water bodies. That is, the water treatment agent of the present invention has the following formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic amine group,
m represents the valence number of the metal atom or 1. ) and the following formula: (In the formula, R 2 represents a hydrogen atom or a methyl group, X 2 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic amine group,
n represents the valence number of the metal atom or 1. ) having a structural unit (B) with a molecular weight of 500~
50,000, and is characterized in that the proportion of the structural unit (A) in the entire copolymer is 0.1 to 2.5 mol%. The water treatment agent of the present invention can be obtained by conventionally known methods. For example, the following formula () forming the structural unit (A): (In the formula, R 1 , X 1 and m have the same meanings as above.) The following formula () forming the compound and structural unit (B) represented by: (In the formula, R 2 , X 2 and n have the same meanings as above.) A compound represented by the formula and optional monomers are added to water in a desired molar ratio to initiate polymerization of peroxide, etc. By adding the agent and heating, it is possible to obtain a water-soluble copolymer consisting of structural units in a corresponding molar ratio, that is, the water treatment agent of the present invention. The compounds represented by the formula () used in the present invention include organic compounds such as allylsulfonic acid and methallylsulfonic acid, their sodium salts, potassium salts, lithium salts, ammonium salts, triethanolamine salts, and alkylamine salts. Examples include amine salts. Examples of the compound represented by the formula () include acrylic acid, methacrylic acid, and organic amine salts thereof such as sodium salts, potassium salts, lithium salts, ammonium salts, triethanolamine salts, and alkylamine salts. In the water treatment agent of the present invention, in addition to the structural units (A) and (B), another structural unit (C) may also be used as necessary.
Examples of monomers forming structural units (C) other than structural units (A) and (B) include itaconic acid, fumaric acid,
Examples include acrylamide, acrylic acid ester, vinyl acetate, styrene, ethylene oxide, hydroxyalkyl acrylate, acrylonitrile, ethylene, n-butylene, isobutylene, vinylsulfonic acid, styrylsulfonic acid, and the like. The structural unit (C) is not limited to one type, and may be two or more types. Considering the effects of the copolymer of the present invention,
It is necessary that the molecular weight is 500 to 50,000, and particularly preferably 500 to 10,000. Similarly, the proportion of structural unit (A) in the entire copolymer is
It is necessary to be 0.1 to 2.5 mol%, especially,
It is preferably 0.1 mol% or more and less than 1.0 mol%. In the present invention, when a structural unit (C) other than structural units (A) and (B) is formed, the proportion of the structural unit (C) in the entire copolymer is generally from 0.1 to
It is preferably 10 mol%, particularly 0.1 to 2.5 mol%. The water treatment agent of the present invention contains the above-mentioned copolymer as an active ingredient, and is used by directly or continuously or intermittently adding it to the target water system in the same way as conventional water treatment agents. The water treatment agent of the present invention can be applied to all types of water such as pure water, soft water, tap water, and industrial water, and the concentration used is determined depending on the purpose, but generally the active ingredient is 0.1 to 500 ppm. Yes, especially
It is preferably 0.5 to 200 ppm. In addition, there is no particular restriction on the PH range of the target water system, but it is generally PH6~
14, preferably PH6-12. Specific examples of target water systems include boiler water systems, open or closed circulation cooling water systems, one-time cooling water systems,
Examples include brine water systems, some converter dust collection water systems, cooling water systems for dry pits such as blast furnace converters, ammonia distillation tower water systems in coke factories, etc., incineration ash water systems in municipal garbage incineration plants, and seawater desalination equipment. In addition, in recent years, highly concentrated operations that result in high calcium hardness water systems have often been carried out in circulating cooling water systems, but such highly concentrated operations have a rather unique scale prevention effect for the water treatment agent of the present invention. This is preferable because it provides the conditions for obtaining. On the other hand, in cooling water systems that use especially pure water or soft water, there are few dissolved salts, which gives the water treatment agent of the present invention a rather unique anti-corrosion effect compared to conventional water treatment agents. It is preferable because it exhibits an excellent corrosion inhibiting effect. The water treatment agent of the present invention is sufficiently effective for water systems made of steel or other materials even when used alone, but if other metals are also used, other water treatment agents may be used as necessary. For example, oxycarboxylic acids; thiazoles such as mercaptobenzothiazole; azoles such as benzotriazole; water-soluble amines such as hydrazine, cyclohexylamine, alkylamine, alkanolamine, polyamine; ethyleneimine, pyrrolidine, piperidine, piperazine, Imines such as ketimine; hydroxamic acids such as formhydroxamic acid, acetohydroxamic acid, and benzhydroxysamic acid; long-chain aliphatic carboxylic acids such as oleic acid; benzoic acid,
Organic compounds such as aromatic carboxylic acids such as phthalic acid; catechols; tannins; lignins; phosphonic acids; nitrites, silicates, various phosphates, borates, zinc salts, nickel salts, molybdenum salts , inorganic salts such as aluminum salts, aluminates, tungsten salts, and vanadium salts may be used in combination. In addition, other known scale inhibitors and slime control agents may be used in combination, if necessary. The water treatment agent of the present invention can effectively suppress scale formation even in water systems with high calcium hardness, where scale formation cannot be effectively suppressed with conventional water treatment agents. . Furthermore, the water treatment agent of the present invention has low toxicity, does not cause eutrophication, and is not easily decomposed by microorganisms, so it has low BOD.
It also has the advantage of not becoming a source. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Add 300 ppm of CaCl 2 2H 2 O (in terms of CaCO 3 ) and 300 ppm of NaHCO 3 (in terms of CaCO 3 ) to desalinated water, adjust the pH to 9.1, put 500 ml of the test solution into an Erlenmeyer flask, and add After adding 20 ppm of the water treatment agent listed in Table 1 (all sodium salts) and sealing the container, it was immersed in a constant-temperature water bath with a water temperature of 50° C. and allowed to stand for 20 hours. Next, this test solution was passed through a 0.1μ membrane filter, and the concentration of calcium ions in the solution was measured by the EDTA method. The results are shown in Table 1.
【表】
この結果から、本発明の水処理剤（ケースNo.１
〜５）が、炭酸カルシウムの析出を抑制する効果
についても従来品（ケースNo.10）に比べて極めて
優れていることがわかる。また、構造単位(A)の共
重合体全体に占める割合が５モル％の水処理剤
（ケースNo.７）及び分子量が70000の水処理剤（ケ
ースNo.８）の効果は、本発明の水処理剤よりも著
しく劣ることがわかる。なお、ケースNo.１におい
て、構造単位(A)の構成割合を変えずに、構造単位
(B)の一部（共重合体全体に占める割合として2.5
モル％）に更に他の構造単位(C)であるアクリルア
ミド又はイタコン酸を付加したもの（三元共重合
体）についても同様の試験を行なつたところ、ケ
ースNo.１と同様の結果を得た。
実施例 ２
次の組成の合成海水を調製した（但し、この合
成水は海水の２倍濃縮水に相当する）。
CaCl2・2H2O 2000ppm（CaCO3換算量）
NaHCO3 250ppm（CaCO3換算量）
NaCl 60000ppm
Na2SO4 7500ppm
PH＝8.5
上記合成海水500mlを三角フラスコに入れ、更
に第２表記載の水処理剤（但し、いずれも分子量
3000のナトリウム塩）を所定量添加し、密栓した
後、水温60℃の恒温水槽中に浸漬し、20時間静置
した。次に、フラスコを取り出し、試験液の濁り
や沈澱物の有無を目視により観察した。結果を第
２表に示す。
この結果から、本発明の水処理剤（ケースNo.１
〜４）が合成海水中におけるスケールの析出を抑
制する効果についても、従来品（ケースNo.５，
６）に比べ、極めて優れていることがわかる。[Table] From this result, the water treatment agent of the present invention (Case No. 1
It can be seen that samples 5) to 5) are extremely superior to the conventional product (Case No. 10) in terms of the effect of suppressing the precipitation of calcium carbonate. Furthermore, the effects of the water treatment agent in which the proportion of the structural unit (A) in the entire copolymer is 5 mol % (Case No. 7) and the water treatment agent in which the molecular weight is 70,000 (Case No. 8) are as follows. It can be seen that it is significantly inferior to water treatment agents. In addition, in case No. 1, the structural unit (A) is
Part of (B) (2.5% as a proportion of the entire copolymer)
When a similar test was conducted on a product (terpolymer) in which another structural unit (C), acrylamide or itaconic acid, was added to (mol%), the same results as Case No. 1 were obtained. Ta. Example 2 Synthetic seawater having the following composition was prepared (however, this synthetic water corresponds to twice concentrated seawater). CaCl 2・2H 2 O 2000ppm (CaCO 3 equivalent amount) NaHCO 3 250ppm (CaCO 3 equivalent amount) NaCl 60000ppm Na 2 SO 4 7500ppm PH=8.5 Pour 500 ml of the above synthetic seawater into an Erlenmeyer flask, and further water treatment as described in Table 2. agent (however, molecular weight
After adding a predetermined amount of sodium salt (3000) and sealing the container, the container was immersed in a constant temperature water bath with a water temperature of 60° C. and allowed to stand for 20 hours. Next, the flask was taken out and the test liquid was visually observed for turbidity and the presence of precipitates. The results are shown in Table 2. From this result, the water treatment agent of the present invention (Case No. 1
Regarding the effect of ~4) on suppressing scale precipitation in synthetic seawater, conventional products (Case No. 5,
It can be seen that this is extremely superior compared to 6).
【表】【table】
【表】
実施例 ３
第３表に記載の各水質を示す試験液１をビー
カーにとり、これに本発明の水処理剤（但し、い
ずれもナトリウム塩）を所定量加え、水温を50℃
に保持した。このビーカーに軟鋼製テストピース
を撹拌棒に懸吊し、160rpmの回転速度で回転さ
せながら５日間その状態を維持した。[Table] Example 3 Test liquid 1 showing each water quality listed in Table 3 was placed in a beaker, a predetermined amount of the water treatment agent of the present invention (all sodium salts) was added thereto, and the water temperature was raised to 50°C.
was held at A mild steel test piece was suspended from a stirring rod in this beaker and maintained in that state for 5 days while rotating at a rotational speed of 160 rpm.
【表】【table】
【表】
なお、第３表において１の水質は密閉循環式冷
却水系、低濃縮開放循環冷却水系、２の水質は約
３倍濃縮開放循環冷却水系に相当する。
結果を第４表に示す。[Table] In Table 3, water quality 1 corresponds to a closed circulation cooling water system, a low concentration open circulation cooling water system, and water quality 2 corresponds to an approximately 3 times concentrated open circulation cooling water system. The results are shown in Table 4.
【表】
この結果から、比較例として示した薬剤に比べ
本発明の水処理剤は極めて優れた腐食抑制効果を
有することがわかる。
実施例 ４
試験水として導電率１μＳ／cm以下の純水を用
いた以外は、実施例３と同様の操作により腐食試
験を行なつた。結果を第５表に示す。
この結果から明らかに本発明の水処理剤は、塩
類濃度が極めて低い純水系においても、比較例と
して示した薬剤に比べ優れた腐食抑制効果を有す
ることがわかる。[Table] From the results, it can be seen that the water treatment agent of the present invention has an extremely superior corrosion inhibiting effect compared to the agents shown as comparative examples. Example 4 A corrosion test was conducted in the same manner as in Example 3, except that pure water with a conductivity of 1 μS/cm or less was used as the test water. The results are shown in Table 5. These results clearly show that the water treatment agent of the present invention has a superior corrosion inhibiting effect compared to the agents shown as comparative examples, even in pure water systems with extremely low salt concentrations.
Claims (1)
し、X1は水素原子、一価若しくは二価の金属原
子、アンモニウム基又は有機アミン基を表わし、
ｍは金属原子の価数又は１を表わす。） で示される構造単位(A)と、 次式： （式中、R2は水素原子又はメチル基を表わ
し、X2は水素原子、一価若しくは二価の金属原
子、アンモニウム基又は有機アミン基を表わし、
ｎは金属原子の価数又は１を表わす。） で示される構造単位(B)とを有する分子量500〜
50000の水溶性共重合体であつて、かつ、構造単
位(A)の共重合体全体に占める割合が0.1〜2.5モル
％であることを特徴とする水処理剤。 ２ 構造単位(A)の共重合体全体に占める割合が
0.1モル％以上1.0モル％未満である特許請求の範
囲第１項記載の水処理剤。[Claims] Primary formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic amine group,
m represents the valence number of the metal atom or 1. ) and the following formula: (In the formula, R 2 represents a hydrogen atom or a methyl group, and X 2 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic amine group,
n represents the valence number of the metal atom or 1. ) having a molecular weight of 500 or more and the structural unit (B) shown in
50,000 water-soluble copolymer, and the proportion of the structural unit (A) in the entire copolymer is 0.1 to 2.5 mol%. 2 The proportion of the structural unit (A) in the entire copolymer is
The water treatment agent according to claim 1, which contains 0.1 mol% or more and less than 1.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21538982A JPS59105892A (en) | 1982-12-10 | 1982-12-10 | Agent for treatment of water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21538982A JPS59105892A (en) | 1982-12-10 | 1982-12-10 | Agent for treatment of water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59105892A JPS59105892A (en) | 1984-06-19 |
| JPS6247434B2 true JPS6247434B2 (en) | 1987-10-07 |
Family
ID=16671493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21538982A Granted JPS59105892A (en) | 1982-12-10 | 1982-12-10 | Agent for treatment of water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59105892A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6440736U (en) * | 1987-09-05 | 1989-03-10 | ||
| JPH02167109A (en) * | 1988-07-11 | 1990-06-27 | Milliken Res Corp | Dust-removing mat having hem part |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ213578A (en) * | 1984-11-09 | 1988-04-29 | Calgon Corp | Inhibiting corrosion and scale deposition in aqueous systems by adding water soluble polymers |
| JPS63156599A (en) * | 1986-12-08 | 1988-06-29 | ザ ビー．エフ．グッドリッチ カンパニー | Method of treating aqueous medium by copolymer containing acrylic amide alkane sulfonic acid |
| EP0297049B1 (en) * | 1987-06-23 | 1991-01-16 | Ciba-Geigy Ag | Scale inhibition |
| WO2014157462A1 (en) * | 2013-03-27 | 2014-10-02 | 栗田工業株式会社 | Method and agent for treating water in cooling water system |
| JP5682727B2 (en) * | 2014-08-06 | 2015-03-11 | 栗田工業株式会社 | Water treatment method and water treatment agent for cooling water system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5712895A (en) * | 1980-06-26 | 1982-01-22 | Kurita Water Ind Ltd | Water-disposing agent |
| JPS5728122A (en) * | 1980-06-09 | 1982-02-15 | Rhone Poulenc Ind | Novel polymer composition and use for preventing water incrustation generation |
-
1982
- 1982-12-10 JP JP21538982A patent/JPS59105892A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5728122A (en) * | 1980-06-09 | 1982-02-15 | Rhone Poulenc Ind | Novel polymer composition and use for preventing water incrustation generation |
| JPS5712895A (en) * | 1980-06-26 | 1982-01-22 | Kurita Water Ind Ltd | Water-disposing agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6440736U (en) * | 1987-09-05 | 1989-03-10 | ||
| JPH02167109A (en) * | 1988-07-11 | 1990-06-27 | Milliken Res Corp | Dust-removing mat having hem part |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59105892A (en) | 1984-06-19 |
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