JP4711902B2 - ボイラ腐食抑制方法 - Google Patents
ボイラ腐食抑制方法 Download PDFInfo
- Publication number
- JP4711902B2 JP4711902B2 JP2006199218A JP2006199218A JP4711902B2 JP 4711902 B2 JP4711902 B2 JP 4711902B2 JP 2006199218 A JP2006199218 A JP 2006199218A JP 2006199218 A JP2006199218 A JP 2006199218A JP 4711902 B2 JP4711902 B2 JP 4711902B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- boiler
- corrosion
- morpholine
- alkoxyalkylamine
- 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.)
- Active
Links
- 238000005260 corrosion Methods 0.000 title claims description 77
- 230000007797 corrosion Effects 0.000 title claims description 77
- 238000000034 method Methods 0.000 title claims description 46
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 82
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 42
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 29
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- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 7
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 claims description 5
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 claims description 5
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 claims description 5
- VGEMYWDUTPQWBN-UHFFFAOYSA-N n-ethyl-2-methoxyethanamine Chemical compound CCNCCOC VGEMYWDUTPQWBN-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- QAFODUGVXFNLBE-UHFFFAOYSA-N 1-methoxybutan-2-amine Chemical compound CCC(N)COC QAFODUGVXFNLBE-UHFFFAOYSA-N 0.000 claims description 3
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- -1 iron ions Chemical class 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 230000002829 reductive effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 229940123973 Oxygen scavenger Drugs 0.000 description 3
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- ARJYMGOQJFRJEF-UHFFFAOYSA-N 2-methoxy-n-methylpropan-1-amine Chemical compound CNCC(C)OC ARJYMGOQJFRJEF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- RHXLLSRWRDBDMY-UHFFFAOYSA-N (2-methylpropan-2-yl)oxymethanamine Chemical compound CC(C)(C)OCN RHXLLSRWRDBDMY-UHFFFAOYSA-N 0.000 description 1
- HNZKEVBWMXMMBH-UHFFFAOYSA-N 1-ethoxy-n,n-dimethylmethanamine Chemical compound CCOCN(C)C HNZKEVBWMXMMBH-UHFFFAOYSA-N 0.000 description 1
- RLEWPIDGRLZEPU-UHFFFAOYSA-N 1-ethoxy-n-methylmethanamine Chemical compound CCOCNC RLEWPIDGRLZEPU-UHFFFAOYSA-N 0.000 description 1
- ILRZBPLDJKEWRW-UHFFFAOYSA-N 1-ethoxyethanamine Chemical compound CCOC(C)N ILRZBPLDJKEWRW-UHFFFAOYSA-N 0.000 description 1
- BEDBBXLHMLEAGG-UHFFFAOYSA-N 1-ethoxypropan-1-amine Chemical compound CCOC(N)CC BEDBBXLHMLEAGG-UHFFFAOYSA-N 0.000 description 1
- IOBNOWOMHKTRIL-UHFFFAOYSA-N 1-methoxy-2-methylpropan-1-amine Chemical compound COC(N)C(C)C IOBNOWOMHKTRIL-UHFFFAOYSA-N 0.000 description 1
- BGGVJKGMDWLNRC-UHFFFAOYSA-N 1-methoxy-n,n-dimethylethanamine Chemical compound COC(C)N(C)C BGGVJKGMDWLNRC-UHFFFAOYSA-N 0.000 description 1
- YFTNTMQKPLVKFQ-UHFFFAOYSA-N 1-methoxy-n,n-dimethylmethanamine Chemical compound COCN(C)C YFTNTMQKPLVKFQ-UHFFFAOYSA-N 0.000 description 1
- LDCZMVCTWDIRAI-UHFFFAOYSA-N 1-methoxy-n-(methoxymethyl)-n-methylmethanamine Chemical compound COCN(C)COC LDCZMVCTWDIRAI-UHFFFAOYSA-N 0.000 description 1
- JAKDCRZCZAETHF-UHFFFAOYSA-N 1-methoxy-n-methylethanamine Chemical compound CNC(C)OC JAKDCRZCZAETHF-UHFFFAOYSA-N 0.000 description 1
- YNVUTAPHFZKPBN-UHFFFAOYSA-N 1-methoxy-n-methylmethanamine Chemical compound CNCOC YNVUTAPHFZKPBN-UHFFFAOYSA-N 0.000 description 1
- NASSELZHMMRSRS-UHFFFAOYSA-N 1-methoxy-n-methylpropan-1-amine Chemical compound CCC(NC)OC NASSELZHMMRSRS-UHFFFAOYSA-N 0.000 description 1
- ZAJYRMCZVGRVKJ-UHFFFAOYSA-N 1-methoxybutan-1-amine Chemical compound CCCC(N)OC ZAJYRMCZVGRVKJ-UHFFFAOYSA-N 0.000 description 1
- MHVSMFDBVMPRGT-UHFFFAOYSA-N 1-methoxyethanamine Chemical compound COC(C)N MHVSMFDBVMPRGT-UHFFFAOYSA-N 0.000 description 1
- KNYKHCLCBHSFCK-UHFFFAOYSA-N 1-methoxypropan-1-amine Chemical compound CCC(N)OC KNYKHCLCBHSFCK-UHFFFAOYSA-N 0.000 description 1
- NXMXETCTWNXSFG-UHFFFAOYSA-N 1-methoxypropan-2-amine Chemical compound COCC(C)N NXMXETCTWNXSFG-UHFFFAOYSA-N 0.000 description 1
- PBRPPWLCSOOWJO-UHFFFAOYSA-N 1-propan-2-yloxyethanamine Chemical compound CC(C)OC(C)N PBRPPWLCSOOWJO-UHFFFAOYSA-N 0.000 description 1
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 1
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- KOHBEDRJXKOYHL-UHFFFAOYSA-N 2-methoxy-n-methylethanamine Chemical compound CNCCOC KOHBEDRJXKOYHL-UHFFFAOYSA-N 0.000 description 1
- VUZDMYKIULCESL-UHFFFAOYSA-N 2-methoxybutan-1-amine Chemical compound CCC(CN)OC VUZDMYKIULCESL-UHFFFAOYSA-N 0.000 description 1
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- USECIYVEPXUVHT-UHFFFAOYSA-N 2-propan-2-yloxyethanamine Chemical compound CC(C)OCCN USECIYVEPXUVHT-UHFFFAOYSA-N 0.000 description 1
- HMWXCSCBUXKXSA-UHFFFAOYSA-N 2-propoxyethanamine Chemical compound CCCOCCN HMWXCSCBUXKXSA-UHFFFAOYSA-N 0.000 description 1
- QKCOKEIMHOFEHO-UHFFFAOYSA-N 3-methoxy-2-methylpropan-1-amine Chemical compound COCC(C)CN QKCOKEIMHOFEHO-UHFFFAOYSA-N 0.000 description 1
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- IQKTYAYBZRHHJI-UHFFFAOYSA-N 3-methoxybutan-1-amine Chemical compound COC(C)CCN IQKTYAYBZRHHJI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
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- RKSGFMRROMRUPP-UHFFFAOYSA-N butan-2-yloxymethanamine Chemical compound CCC(C)OCN RKSGFMRROMRUPP-UHFFFAOYSA-N 0.000 description 1
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- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
(1)給水系統に設置したpH計の測定値をもとにpHが設定範囲になるように薬液注入ポンプ等を用いて注入する方法、
(2)電気伝導率とpHの関係を予め求めておき、給水系統に設置した電気伝導率計の測定値をもとに、pHの設定範囲に相当する電気伝導率の設定範囲になるように薬液注入ポンプ等を用いて注入する方法、
等がある。この場合、薬液注入を自動注入方法としてもよい。
本発明の腐食抑制方法において、貫流ボイラ以外の固形分の混入が許容できるボイラシステムでは、ボイラ水のpHを調整するためにアルカリ金属水酸化物、リン酸塩から選択される1種以上の化合物と併用しても良い。蒸気圧力が3MPaを超えるボイラでは、水酸化カリウムやリン酸カリウム等のカリウム塩を使用するとアルカリ腐食が発生し易くなるため、アルカリ金属水酸化物としては水酸化ナトリウム、リン酸塩としては第2リン酸ナトリウム、第3リン酸ナトリウム、トリポリリン酸ナトリウム等のナトリウム塩を使用するのが好ましい。
・A−1:3−メトキシプロピルアミン(試薬、関東化学(株)製)
・A−2:2−メトキシエチルアミン(試薬、関東化学(株)製)
・A−3:1−メトキシ−sec−ブチルアミン(試薬、関東化学(株)製)
・A−4:2−エトキシエチルアミン(試薬、関東化学(株)製)
・A−5:3−エトキシプロピルアミン(試薬、関東化学(株)製)
・A−6:N−(2−メトキシエチル)エチルアミン(試薬、関東化学(株)製)
・B−1:モルホリン(試薬、関東化学(株)製)
・C−1:2−アミノエタノール(試薬、関東化学(株)製)
・D−1:シクロヘキシルアミン(試薬、関東化学(株)製)
・D−2:アンモニア(試薬、関東化学(株)製)
400番研磨紙で研磨仕上げした寸法が1×13×75mmの低炭素鋼試験片(材質:JIS G3141 SPCC−SB)とアルミニウム黄銅製試験片(材質:JIS H3100 C6871)をアセトンで脱脂後、乾燥して試験前の質量を測定した。四日市市水をミリポア社製Milli-Qプラスシステム(商品名)に通水して得られたイオン交換水(比抵抗18MΩ・cm)に表1に示す腐食抑制剤を添加してpH(25℃)を9.4に調整して試験液として用いた。試験液100mLと試験片1枚を密閉容器に入れ、窒素ガスを通気して試験液の溶存酸素濃度を10μg/Lまで低下させた後、密閉して温度70℃で7日間保持した。7日後、試験片を取り出して付着物を除去後、試験後の質量を測定し、下記式より腐食速度(mdd)を計算した。結果を表1に示す。
腐食速度(mdd)=(W0−W1)/(S×T)
W0:試験前の質量(mg)、W1:試験後の質量(mg)
S:試験片の表面積(dm2)
T:試験期間(日数)
蒸気圧10MPaの試験ボイラにおいて、四日市市水を強酸性陽イオン交換樹脂〔ダウエックス マラソンC(商品名、ダウケミカル社製)〕と強塩基性陰イオン交換樹脂〔ダウエックス マラソンA(商品名、ダウケミカル社製)〕を含む混床式イオン交換水製造装置に通水して得られたイオン交換水(電気伝導率0.2μS/cm以下)を補給水に使用し、給水中の溶存炭酸濃度は0.1ppm、ブロー率は2%としてボイラを運転した。腐食防止剤を給水に対して3mg/L添加し、その時の給水、ボイラ水、蒸気の初期凝縮水、復水の各pH(25℃)を測定した。蒸気の初期凝縮部のpHは、蒸気の湿り度が2%の箇所における凝縮水のpHとした。結果を表2に示す。
蒸気圧力11MPa、蒸気量200t/hの水管式自然循環ボイラーにおいて本発明の腐食抑制方法の実機試験を実施した。該ボイラシステムにおけるボイラドラム、蒸発管、エコノマイザー、脱気器、給水系統や蒸気・復水系統の各種配管等の主要な構成材質は低炭素鋼であった。復水器と給水予熱器の伝熱管の材質はアルミニウム黄銅(JIS H3100 C6871)であった。四日市工業用水を2床3塔式モノベッドポリッシャー式イオン交換水製造装置に通水して得られたイオン交換水(電気伝導率0.2μS/cm以下)をボイラ補給水として使用し、給水中の溶存酸素濃度は0.007mg/Lであった。3−メトキシプロピルアミンを70重量%とモルホリンを30重量%含む組成物を補給水量に対して2.4mg/L添加した。第三リン酸ソーダと第二リン酸ソーダをNa/PO4のモル比が2.6になるように配合比を調整した混合物をボイラドラムに添加して、ボイラ水のPO4濃度が0.5〜2mg/Lになるように調整した。ボイラーのブロー率は2%、復水回収率は60%であった。試験期間中は脱気器出口の給水、ボイラ水、復水を週1回毎にサンプリングして、JIS B8224:2005『ボイラの給水及びボイラ水−試験方法』の方法に基づき各サンプルのpH(pH計)、鉄濃度(2、4、6−トリ−2−ピリジル−1、3、5−トリアジン吸光光度法)、銅濃度(ICP発光分光分析法)をそれぞれ測定した。比較例として3−メトキシプロピルアミンとモルホリンの混合物の替わりにモルホリンを単独で補給水量に対して6mg/L添加して同様に実施した。各試験の試験期間は30日間として、各測定項目の平均値を求めた。鉄濃度と銅濃度がいずれも10μg/L以下であれば、良好と判断した。結果を表3に示す。
Claims (3)
- 補給水としてイオン交換水を使用し、鋼材と銅合金を含むボイラシステムの腐食抑制方法において、(A)炭素数が3〜5のアルコキシアルキルアミンと(B)モルホリンを80:20〜20:80の重量比でボイラシステム水系に添加し、当該給水のpH(25℃)を9.0〜9.5に調整することを特徴とする、鋼材と銅合金の腐食を同時に防止するボイラの腐食抑制方法。
- (A)成分、(B)成分と共に(C)2−アミノエタノールを添加するボイラの腐食抑制方法であって、(A)成分と(B)成分の合計量に対して、(C)2−アミノエタノールを100:1〜100:10の重量比で添加することを特徴とする請求項1記載のボイラの腐食抑制方法。
- (A)成分が3−メトキシプロピルアミン、2−メトキシエチルアミン、1−メトキシ−sec−ブチルアミン、2−エトキシエチルアミン、3−エトキシプロピルアミン、N−(2−メトキシエチル)エチルアミンから選ばれた1種以上である請求項1又は請求項2のいずれかに記載のボイラの腐食抑制方法。
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JP2004211195A (ja) * | 2002-11-12 | 2004-07-29 | Kurita Water Ind Ltd | 金属防食剤、金属防食方法、原油常圧蒸留装置における塩化水素発生防止剤および塩化水素発生防止方法 |
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JPH05212372A (ja) * | 1991-11-06 | 1993-08-24 | Nalco Chem Co | ボイラー水の脱酸素法 |
JPH07180073A (ja) * | 1993-09-28 | 1995-07-18 | Nalco Chem Co | 湿り炭化水素凝縮装置における塩化物腐食を抑制するためにアミン配合物を使用する方法 |
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