JP6896693B2 - 溶解除去組成物および洗浄方法 - Google Patents
溶解除去組成物および洗浄方法 Download PDFInfo
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- JP6896693B2 JP6896693B2 JP2018225137A JP2018225137A JP6896693B2 JP 6896693 B2 JP6896693 B2 JP 6896693B2 JP 2018225137 A JP2018225137 A JP 2018225137A JP 2018225137 A JP2018225137 A JP 2018225137A JP 6896693 B2 JP6896693 B2 JP 6896693B2
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- 150000007513 acids Chemical class 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
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- 150000001413 amino acids Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 description 1
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- 239000004202 carbamide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical class [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
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- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
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- AIJZIRPGCQPZSL-UHFFFAOYSA-N ethylenetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)=C(C(O)=O)C(O)=O AIJZIRPGCQPZSL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- DOGJSOZYUGJVKS-UHFFFAOYSA-N glyceryl monothioglycolate Chemical compound OCC(O)COC(=O)CS DOGJSOZYUGJVKS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BKIFJPAJPVNRSG-UHFFFAOYSA-N oxolane-2,2,5,5-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC(C(O)=O)(C(O)=O)O1 BKIFJPAJPVNRSG-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- ULZHJTRNULBXJF-UHFFFAOYSA-N sodium;1,3,4-thiadiazolidine-2,5-dithione Chemical compound [Na].S=C1NNC(=S)S1 ULZHJTRNULBXJF-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- 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
- C23F11/10—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 using organic inhibitors
- C23F11/16—Sulfur-containing compounds
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
また、本開示は、母材に付着した金属酸化物を含むスケールを溶解除去する主剤と、酸素還元性を有する有機酸である第1還元剤と、チオ尿素系化合物、二酸化チオ尿素系化合物、チオグリコール酸塩および亜ジチオン酸塩から少なくとも1種選択される第2還元剤と、メルカプタン基(−HS)、チオシアン酸基(−SCN)もしくはメルカプタン基のアルカリ金属塩(NaS−、KS−、LiS−)のいずれかを有する硫黄有機化合物から選ばれる少なくとも1種のインヒビターと、を含む溶解除去組成物を提供する。
また、本開示の一態様では、母材に付着した金属酸化物を含むスケールを溶解除去する主剤と、酸素還元性を有する有機酸である第1還元剤と、チオ尿素系化合物、二酸化チオ尿素系化合物、チオグリコール酸塩および亜ジチオン酸塩から少なくとも1種選択される第2還元剤と、両性界面活性剤と、非イオン界面活性剤と、を含む溶解除去組成物を提供しうる。
第1還元剤の配合量は、溶解除去組成物の全質量に対して、0.01質量%以上8質量%以下、好ましくは0.1質量%以上5質量%以下、より好ましくは0.5質量%以上3質量%以下である。0.01%質量%未満ではスケール溶解性が不十分となる(後に記載の比較例12参照)。8質量%を超えると、防食性が不十分となる(後に記載の比較例13参照)。
第2還元剤の配合量は、溶解除去組成物の全質量に対して、0.01質量%以上1質量%以下、好ましくは0.01質量%以上0.1質量%以下、より好ましくは0.02質量%以上0.08質量%以下である。0.01質量%未満ではスケール溶解性が不十分となる(後に記載の比較例10参照)。1質量%を超えると、防食性が不十分となる(後に記載の比較例11参照)。
硫黄有機化合物の配合量は、溶解除去組成物の全質量に対して、0.001質量%以上1質量%以下、好ましくは0.01質量%以上0.1質量%以下、より好ましくは0.005質量%以上0.05質量%以下である。0.001質量%未満だと防食性が不十分となる(後に記載の比較例14参照)。
次に、本実施形態に係る溶解除去組成物の製造方法について説明する。本実施形態に係る溶解除去組成物の製造方法に特に制限はない。上記溶解除去組成物の製造方法としては、例えば、純水又は蒸留水などの水に主剤、第1還元剤、第2還元剤、両性界面活性剤、及び非イオン界面活性剤などの各成分を室温にて順次添加して混合し、KOHなどを添加してpHを5〜8の範囲に調整することにより製造することができる。
ボイラに水を供給しながら、供給配管の一部に各成分を順次添加して溶解除去組成物を調製する場合、第1還元剤を投入し系統内の酸素を還元した後、第2還元剤を投入してスケールを還元するとよい。第1還元剤を投入した後、本実施形態では例えば0.5〜1時間程度で溶存酸素を還元できる。
上記実施形態に係る溶解除去組成物には、スケールの還元溶解能を有する成分が必須である。そこで、主剤に安定に溶解でき、配合時の洗浄液酸化還元電位が−200mV vs SSE以下となる試薬を選定し、それら試薬について、酸化鉄の還元溶解能を確認した。
上記実施形態に係る溶解除去組成物には、酸素還元能を有する成分が必須である。そこで、上記で選定した試薬a〜gについて、酸素還元能を確認した。
ホスホン酸20質量%水溶液に、還元剤、インヒビターおよび酸化鉄を投入して、母材(低合金鋼STBA23、表面積26cm2)を共存させ、大気開放下、40℃で20時間静置した後、酸化鉄還元能および母材防食性について評価した。STBA23は合金鋼管の一種で、ボイラ内の熱交換器やプラント構成機器の熱交換器などにおける熱伝達の役割を果たす規格材料(クロムモリブデン鋼を含有する鉄鋼材料、JISではロックウェル硬さ(HRB)85以下と規定)である。
比較例1:亜ジチオン酸ナトリウム0.05質量%
実施例1:亜ジチオン酸ナトリウム0.05質量%+アスコルビン酸2.0質量%
実施例2:二酸化チオ尿素1.0質量%+アスコルビン酸2.0質量%
上記実施形態に係る溶解除去組成物には、大気開放環境下で安定的に母材腐食を防止できることが望まれる。そこで、大気開放環境の酸素が存在している状態でも母材の腐食を抑制できるインヒビターについて検討した。
I−a:両性界面活性剤A
I−b:非イオン界面活性剤A(ポリオキシアルキレングリコール脂肪酸エステル類)
I−c:硫黄化合物(グアニルチオ尿素)
I−d:脂肪酸(オレイン酸系)
I−e:カチオン型界面活性剤A(塩化ラウリルトリメチルアンモニウム系)
I−f:カチオン型界面活性剤B(塩化ステアリルトリメチルアンモニウム系)
I−g:非イオン界面活性剤B(アルキルフェノールのエチレンオキサイド付加物系)
I−h:非イオン界面活性剤C(アルキルフェノールのエチレンオキサイド付加物系)
I−i:両性界面活性剤B(ヤシ油脂肪酸アミドプロピルベタイン)
I−j:硫黄有機化合物(メルカプトベンゾチアゾール系)
I−k:アミン剤A(トリエタノールアミン系)
I−l:アミン剤B(2−アミノ-メチル−1−プロパノール系)
I−m:アミン剤C(モノイソプロパノールアミン系)
I−n:無機系材料(亜硝酸ナトリウム系)
ホスホン酸20質量%水溶液に、還元剤、インヒビターおよび酸化鉄を投入して、母材(低合金鋼STBA23、表面積26cm2)を共存させ、大気開放下、40℃で20時間静置した後、母材防食性について評価した。
ホスホン酸20質量%水溶液に、還元剤およびインヒビターを投入して、供試体を共存させ(液比は3ml/cm2)、気相部を大気共存密閉環境とし、40℃で100時間緩やかに撹拌した後、共試体断面を顕微鏡で観察した。
還元剤:亜ジチオン酸ナトリウム0.05質量%+アスコルビン酸2質量%
インヒビター:両性界面活性剤A0.2質量%+硫黄有機化合物A,B,C0.02質量%または硫黄有機化合物なし
硫黄有機化合物A:2,5−ジメルカプト−1,3,4−チアジアゾールナトリウム
硫黄有機化合物B:2,4,6−トリメルカプト−S−トリアジンモノナトリウム
硫黄有機化合物C:2−ジブチルアミノ−4,6−ジメルカプト−S−トリアジンモノナトリウム
共試体:ボイラ実機チューブ(付着スケール量10〜15mg/cm2)
主剤(1−ヒドロキシエタン−1,1−ジホスホン酸7質量%)のジホスホン酸を1質量%とした水溶液に、還元剤およびインヒビターを投入して、供試体を共存させ(液比は3ml/cm2)、気相部をN2シールまたは大気共存密閉環境とし、40℃で100時間緩やかに撹拌した後、スケール除去性および母材防食性について評価した。
主剤に、還元剤およびインヒビターを添加し、共試体を共存させ、KOHを用いてpHを調整した。気相部を大気共存密閉環境とし、40℃で30時間緩やかに撹拌した後、スケール除去性および母材防食性について評価した。
還元剤:亜ジチオン酸ナトリウム0.05質量%+アスコルビン酸2質量%
インヒビター:両性界面活性剤A0.2質量%+2,5−ジメルカプト−1,3,4−チアジアゾールナトリウム0.02質量%
共試体:ボイラ実機チューブ(付着スケール量10〜15mg/cm2)
主剤(1−ヒドロキシエタン−1,1−ジホスホン酸7質量%)のジホスホン酸を1質量%とした水溶液に、還元剤およびインヒビターを投入して、供試体を共存させ(液比は3ml/cm2)、KOHを用いてpHを5.5に調整した。気相部を大気共存密閉環境とし、40℃で100時間緩やかに撹拌した後、スケール除去性について評価した。還元剤は、第1還元剤および第2還元剤投入、または、第2還元剤のみ投入とした。
第1還元剤:アスコルビン酸0.1質量%
第2還元剤:亜ジチオン酸ナトリウム0.3質量%
インヒビター:両性界面活性剤A0.1質量%
11 スケール
12 インヒビター
13 露出部
14 孔
Claims (5)
- 母材に付着した金属酸化物を含むスケールを溶解除去する主剤と、
酸素還元性を有する有機酸である第1還元剤と、
チオ尿素系化合物、二酸化チオ尿素系化合物、チオグリコール酸塩および亜ジチオン酸塩から少なくとも1種選択される第2還元剤と、
メルカプタン基(−HS)、チオシアン酸基(−SCN)もしくはメルカプタン基のアルカリ金属塩(NaS−、KS−、LiS−)のいずれかを有する硫黄有機化合物から選ばれる少なくとも1種のインヒビターと、
を含み、
前記主剤は、アミノカルボン酸類、ホスホン酸類およびそれらの塩から選択され、
pHが5〜8である溶解除去組成物。 - 両性界面活性剤と、非イオン界面活性剤と、をさらに含む請求項1に記載の溶解除去組成物。
- 前記有機酸はアスコルビン酸またはエルソルビン酸である請求項1または2に記載の溶解除去組成物。
- 前記第2還元剤は、チオ尿素または二酸化チオ尿素である請求項1から3のいずれかに記載の溶解除去組成物。
- 母材に金属酸化物を含むスケールが付着した洗浄対象を洗浄する方法であって、前記洗浄対象の金属酸化物を含むスケールを溶解除去する主剤および酸素還元性を有する有機酸である第1還元剤で所定時間洗浄した後、チオ尿素系化合物、二酸化チオ尿素系化合物、チオグリコール酸塩および亜ジチオン酸塩から少なくとも1種選択される第2還元剤で洗浄し、前記第2還元剤で溶解除去対象を洗浄した後、露出した前記母材にメルカプタン基(−HS)、チオシアン酸基(−SCN)もしくはメルカプタン基のアルカリ金属塩(NaS−、KS−、LiS−)のいずれかを有する硫黄有機化合物から選ばれる少なくとも1種のインヒビターを接触させ、
前記洗浄はpH5〜8の中性環境で実施し、
前記主剤は、アミノカルボン酸類、ホスホン酸類およびそれらの塩から選択する洗浄方法。
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