JP2013095969A - Agent for inhibiting or suppressing corrosion of ferrous metal and method for inhibiting or suppressing corrosion thereof - Google Patents
Agent for inhibiting or suppressing corrosion of ferrous metal and method for inhibiting or suppressing corrosion thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 91
- 230000007797 corrosion Effects 0.000 title claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002401 inhibitory effect Effects 0.000 title abstract description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title abstract 5
- 150000001412 amines Chemical class 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 24
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 230000005764 inhibitory process Effects 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims description 86
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 74
- 229910052742 iron Inorganic materials 0.000 claims description 33
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005536 corrosion prevention Methods 0.000 claims description 20
- -1 hydroxyethyl group Chemical group 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 9
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 9
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 14
- 230000001629 suppression Effects 0.000 abstract description 8
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000033228 biological regulation Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000010410 layer Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- INAMEDPXUAWNKL-UHFFFAOYSA-N nonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCN INAMEDPXUAWNKL-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 238000012546 transfer Methods 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、鉄系金属の腐食防止又は抑制剤、該剤を用いる鉄系金属の腐食防止又は抑制方法に関する。 The present invention relates to an iron-based metal corrosion preventing or inhibiting agent, and an iron-based metal corrosion preventing or inhibiting method using the agent.
鉄系金属は水分及び酸素の両方が存在することで酸化され腐食が進行する。特に、ボイラ蒸気・復水系では、ボイラから発生した蒸気が熱交換され凝縮水となるが、この凝縮水は多くの炭酸を含む場合はｐＨが低下して腐食が進行し易い。腐食が進行すると鉄系金属管に減肉が生じ、貫孔や割れ等に至ることがある。 Ferrous metals are oxidized and corroded by the presence of both moisture and oxygen. In particular, in a boiler steam / condensate system, steam generated from the boiler is heat-exchanged to become condensed water. When this condensed water contains a large amount of carbonic acid, the pH is lowered and corrosion tends to proceed. When corrosion progresses, the iron-based metal pipe is thinned, which may lead to through holes or cracks.
鉄系金属の腐食を防止又は抑制する１つの方法は、皮膜性アミン(炭素数１２〜２４の飽和又は不飽和の脂肪族アミン化合物)を用いる方法である。皮膜性アミンの腐食防止又は抑制機構は、金属表面にアミノ基が吸着して単分子層又は多分子層の非常に緻密な皮膜を作り、その吸着皮膜によって水分と鉄系金属との接触を防止することで該金属表面の腐食を防止又は抑制する(非特許文献１)。
しかしながら、皮膜性アミンは水に対して非常に溶け難い。皮膜性アミンが安定な溶解状態を保てない場合、成分の変質、分離、沈殿等が起こる可能性があり、そのため能力を十分に発揮できなかったり、蒸気や水中に一部又は全部の成分が注入されなかったり、沈殿物が保管用タンクの底部に堆積したり、蒸気や水中に注入するために使用するポンプ内で詰まりを起こすといった問題が生じることがある。
One method for preventing or suppressing corrosion of iron-based metals is a method using a film-forming amine (saturated or unsaturated aliphatic amine compound having 12 to 24 carbon atoms). Corrosion prevention or suppression mechanism of film-forming amines creates a very dense monolayer or multi-layer film by adsorbing amino groups on the metal surface and prevents contact between moisture and iron-based metal by the adsorbed film. This prevents or suppresses corrosion of the metal surface (Non-patent Document 1).
However, film-forming amines are very insoluble in water. If the film-forming amine cannot maintain a stable dissolved state, the components may be altered, separated, precipitated, etc., so that the ability cannot be fully exhibited, or some or all of the components are present in steam or water. Problems can arise such as not being injected, deposits accumulating at the bottom of the storage tank, and clogging in pumps used for injection into steam or water.
鉄系金属の腐食を防止又は抑制する他の方法として、揮発性アミンを用いる方法がある(非特許文献１)。揮発性アミンは、水に対して非常に溶け易いため、皮膜性アミンを用いる方法について挙げた問題は生じない。揮発性アミンの腐食防止又は抑制機構は、例えばボイラ蒸気・復水系では、注入された揮発性アミンが凝縮水中に溶け込み、系内に存在する酸性物質を中和することで水と接触する鉄系金属の腐食が防止又は抑制され、更に中和対応量以上注入された揮発性アミンによって水のｐＨが上昇することでも腐食が防止又は抑制されるというものである。 As another method for preventing or suppressing corrosion of iron-based metal, there is a method using a volatile amine (Non-patent Document 1). Since volatile amines are very soluble in water, the problems listed for the method using film-forming amines do not occur. For example, in the boiler steam / condensate system, the volatile amine corrosion prevention or suppression mechanism is an iron system in which the injected volatile amine dissolves in the condensed water and neutralizes the acidic substances present in the system to contact the water. The corrosion of the metal is prevented or suppressed, and the corrosion is also prevented or suppressed by increasing the pH of the water by the volatile amine injected more than the amount corresponding to the neutralization.
しかし、気液分配比が低い揮発性アミンは、液相部側ではアミンが溶解し易い性質を示すため腐食を防止又は抑制することができるが、気相部側はアミンが蒸気へ移行し難いため喫水部付近等に腐食が発生しやすいという課題がある。一方、気液分配比が高い揮発性アミンは、気相部側ではアミンが蒸気へ移行し易いため喫水部付近等の腐食を防止又は抑制することができるが、液相部側はアミンが凝縮水へ溶解し難いため腐食が発生し易いという課題がある。
このように、揮発性アミンは選択するアミンによって気液分配比が異なるため、例えばボイラ蒸気・復水系では、気相部から液相部の全ての箇所の腐食を防止又は抑制することは困難である。
However, a volatile amine having a low gas-liquid distribution ratio can prevent or suppress corrosion because the amine easily dissolves on the liquid phase side, but the amine does not easily transfer to vapor on the gas phase side. Therefore, there is a problem that corrosion is likely to occur near the draft section. On the other hand, volatile amines with a high gas-liquid distribution ratio can prevent or suppress corrosion in the vicinity of the draft section, etc., because the amine is easily transferred to the vapor on the gas phase side, but the amine is condensed on the liquid phase side. There is a problem that corrosion is likely to occur because it is difficult to dissolve in water.
Thus, since the volatile amine has a different gas-liquid distribution ratio depending on the selected amine, for example, in a boiler steam / condensate system, it is difficult to prevent or suppress corrosion in all parts from the gas phase to the liquid phase. is there.
この課題を解決するために、気液分配比の異なる複数の揮発性アミンを用いることにより、気相部から液相部の全ての箇所の腐食を防止又は抑制可能なことが知られている。 In order to solve this problem, it is known that the use of a plurality of volatile amines having different gas-liquid distribution ratios can prevent or suppress corrosion of all portions from the gas phase portion to the liquid phase portion.
本発明者らは、気液分配比の異なる複数の揮発性アミンの組合せを鋭意検討した結果、ヘキシルアミンと気液分配比が１０未満の他の揮発性アミンとの組合せが、ヘキシルアミン非配合の組合せよりも予想を遥かに上回る優れた腐食防止又は抑制効果を奏することを見出した。 As a result of intensive investigations of combinations of a plurality of volatile amines having different gas-liquid distribution ratios, the present inventors have found that combinations of hexylamine and other volatile amines having a gas-liquid distribution ratio of less than 10 may contain no hexylamine. The present inventors have found that the corrosion prevention or suppression effect is far superior to that expected from the combination of the above.
したがって、本発明は、ヘキシルアミンと気液分配比が１０未満の他の揮発性アミンとを配合してなることを特徴とする鉄系金属腐食の防止又は抑制剤を提供する。 Accordingly, the present invention provides an iron-based metal corrosion prevention or suppression agent characterized by comprising hexylamine and another volatile amine having a gas-liquid distribution ratio of less than 10.
本発明はまた、上記の腐食防止又は抑制剤を、保護対象の鉄系金属が接する環境中に存在する水及び/又は水蒸気中に混入させることを特徴とする鉄系金属の腐食防止又は抑制方法を提供する。 The present invention also provides a method for preventing or inhibiting corrosion of an iron-based metal, characterized in that the corrosion inhibitor or inhibitor described above is mixed in water and / or water vapor present in the environment in contact with the iron-based metal to be protected. I will provide a.
本発明によれば、気相部から液相部の全ての箇所の腐食を効率的に防止又は抑制することができる。 ADVANTAGE OF THE INVENTION According to this invention, corrosion of all the places from a gaseous-phase part to a liquid phase part can be prevented or suppressed efficiently.
本発明の鉄系金属の腐食防止又は抑制剤は、ヘキシルアミンと気液分配比が１０未満の他の揮発性アミンとを配合してなることを特徴とする。
理論によって本発明が制限されることは意図していないが、本発明の腐食防止又は抑制剤は、その成分たる揮発性アミンが、水/蒸気系において、液相部及び気相部に適切に分配して存在するので、水/蒸気系に接する鉄系金属の気相部、液相部及び喫水部のいずれに対しても腐食を非常に良好に防止又は抑制する。
The iron metal corrosion prevention or inhibitor of the present invention is characterized by blending hexylamine and another volatile amine having a gas-liquid distribution ratio of less than 10.
Although it is not intended that the present invention be limited by theory, the corrosion-inhibiting or inhibiting agent of the present invention is suitable for the volatile amine as a component in the liquid phase part and the gas phase part in a water / steam system. Since they exist in a distributed manner, corrosion is very well prevented or suppressed in any of the gas phase part, liquid phase part and draft part of the iron-based metal in contact with the water / steam system.
本発明において、ヘキシルアミンは、直鎖状のヘキシル基をもつアミンであるモノ-ヘキシルアミン(ＣＨ3(ＣＨ2)4ＣＨ2-ＮＨ2)(以下、単に「ヘキシルアミン」という)及びその塩をいう。塩は、例えば、塩酸塩、硫酸塩、リン酸塩である。 In the present invention, hexylamine is mono-hexylamine (CH 3 (CH 2 ) 4 CH 2 —NH 2 ) (hereinafter simply referred to as “hexylamine”) and its salts, which are amines having a linear hexyl group. Say. Examples of the salt include hydrochloride, sulfate, and phosphate.
本発明の腐食防止又は抑制剤に配合される、ヘキシルアミン以外の他の揮発性アミンは、気液分配比が１０未満である。気液分配比の下限は特に限定されないが、例えば０.１であり得る。
本発明において、揮発性アミンについての気液分配比は、１.０ＭＰａの圧力下で下記式により決定される値とする。
気液分配比＝(気相中の濃度[ｍｇ/Ｌ])／(液相中の濃度[ｍｇ/Ｌ])
気液分配比は、例えば０.１〜８.０であり、好ましくは０.５〜８.０である。
The volatile amine other than hexylamine, which is blended in the corrosion inhibitor or inhibitor of the present invention, has a gas-liquid distribution ratio of less than 10. Although the minimum of a gas-liquid distribution ratio is not specifically limited, For example, it may be 0.1.
In the present invention, the gas-liquid distribution ratio for the volatile amine is a value determined by the following formula under a pressure of 1.0 MPa.
Gas-liquid partition ratio = (concentration in gas phase [mg / L]) / (concentration in liquid phase [mg / L])
The gas-liquid distribution ratio is, for example, 0.1 to 8.0, and preferably 0.5 to 8.0.
揮発性アミンは、アンモニア、ヒドロキシルアミン及びその塩並びにアルカリ性を示す炭素数１〜６の(鎖状又は環状)脂肪族アミン化合物をいう。脂肪族アミン化合物は、一級アミン、二級アミン及び三級アミンのいずれであってもよい。
ヒロドキシルアミンの塩としては、塩酸塩、硫酸塩、リン酸塩が挙げられる。
好ましい鎖状脂肪族アミン化合物は、Ｒ-Ｎ(-Ｒ')-Ｒ”(ここで、Ｒは、ヒドロキシル基、直鎖又は分枝鎖のアルキル基、ヒドロキシアルキル基又はアルコキシ基であり、Ｒ'及びＲ”は、独立して、水素又はアルキル基である。ただし、Ｒ、Ｒ'及びＲ”中の合計炭素数は６を超えない)で表される化合物及びその塩である。上記式中のＲは、１以上のメチル基で置換されていてもよいエチル基、プロピル基、ヒドロキシエチル基又はヒドロキシプロピル基であることがより好ましく、１以上のメチル基で置換されていてもよいヒドロキシエチル基又はヒドロキシプロピル基であることがより好ましく、１以上のメチル基で置換されていてもよいヒドロキシエチル基であることが更に好ましい。Ｒ'及びＲ”は、独立して、水素、メチル基又はエチル基であることがより好ましい。塩は、例えば、塩酸塩、硫酸塩、リン酸塩である。
The volatile amine refers to ammonia, hydroxylamine and a salt thereof, and a C1-C6 (chain or cyclic) aliphatic amine compound exhibiting alkalinity. The aliphatic amine compound may be any of primary amine, secondary amine and tertiary amine.
Examples of the salt of hydroxylamine include hydrochloride, sulfate, and phosphate.
Preferred chain aliphatic amine compounds are RN (—R ′) — R ″ (where R is a hydroxyl group, a linear or branched alkyl group, a hydroxyalkyl group or an alkoxy group, and R 'And R "are independently hydrogen or an alkyl group, provided that the total number of carbon atoms in R, R' and R" does not exceed 6) and salts thereof. R in the group is more preferably an ethyl group, a propyl group, a hydroxyethyl group or a hydroxypropyl group which may be substituted with one or more methyl groups, and a hydroxy group which may be substituted with one or more methyl groups. It is more preferably an ethyl group or a hydroxypropyl group, and further preferably a hydroxyethyl group optionally substituted with one or more methyl groups. R ′ and R ″ are independently hydrogen, methyl group Or And more preferably a group. Examples of the salt include hydrochloride, sulfate, and phosphate.
好ましい環状脂肪族アミン化合物としては、１つ若しくは２つのメチル基若しくはメトキシ基又は１つのエチル基若しくはエトキシ基で置換されていてもよいモルホリンが挙げられ、中でもモルホリン、Ｎ-メチルモルホリン及びＮ-エチルモルホリンが好ましく、モルホリンが更に好ましい。
気液分配比が１０未満の揮発性アミンは、最も好ましくは２-アミノエタノール、１-アミノ-２-プロパノール、２-アミノ-２-メチル-１-プロパノール、モルホリン、アンモニア及びジエチルアミノエタノールからなる群より選択される。
Preferred cycloaliphatic amine compounds include morpholine optionally substituted with one or two methyl or methoxy groups or one ethyl or ethoxy group, among which morpholine, N-methylmorpholine and N-ethyl. Morpholine is preferred, and morpholine is more preferred.
Volatile amines with a gas-liquid partition ratio of less than 10 are most preferably composed of 2-aminoethanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, morpholine, ammonia and diethylaminoethanol. More selected.
本発明の腐食防止又は抑制剤において、ヘキシルアミン以外の他の揮発性アミンとして、揮発性アミンは１種類を単独で用いてもよいし、２種以上の組合せを用いてもよい。
ヘキシルアミンと他の揮発性アミンとの配合率(重量比)は、好ましくは１：５〜１：９９、より好ましくは１：９〜１：９９である。
ヘキシルアミンは臭気物質であるが、本発明の腐食防止又は抑制剤におけるヘキシルアミンの配合率は、上記のように、他の揮発性アミンの配合率に比して、意外にも低くてよいので、腐食防止又は抑制剤としての臭気が抑えられる。このため、本発明の腐食防止又は抑制剤は、環境(例えば、作業環境や周囲環境)に対してやさしい。
In the corrosion inhibitor or inhibitor of the present invention, as the volatile amine other than hexylamine, one type of volatile amine may be used alone, or a combination of two or more types may be used.
The mixing ratio (weight ratio) of hexylamine and other volatile amines is preferably 1: 5 to 1:99, more preferably 1: 9 to 1:99.
Although hexylamine is an odorous substance, the mixing ratio of hexylamine in the corrosion inhibitor or inhibitor of the present invention may be unexpectedly lower than the mixing ratio of other volatile amines as described above. The odor as a corrosion inhibitor or inhibitor is suppressed. For this reason, the corrosion inhibitor or inhibitor of the present invention is friendly to the environment (for example, the work environment and the surrounding environment).
本発明の腐食防止又は抑制剤は、更に水を含んでなる溶液の形態であり得る。水の割合は、例えば、腐食防止又は抑制剤の全重量に対して０〜９９重量％であり得る。 The corrosion inhibitor or inhibitor of the present invention may be in the form of a solution further comprising water. The proportion of water can be, for example, 0 to 99% by weight relative to the total weight of the corrosion inhibitor or inhibitor.
本発明の腐食防止又は抑制剤が対象とする鉄系金属とは、鉄を主成分(含有する金属の中で最も含有量が多い；好ましくは５０重量％以上)とする金属のことであり、金属中の鉄の割合は限定されるものではない。鉄系金属は、化学的な形態として、例えば、鉄(Ｆｅ)、酸化鉄(ＦｅＯ、Ｆｅ2Ｏ3、Ｆｅ3Ｏ4)、オキシ水酸化鉄(ＦｅＯＯＨ)、水酸化鉄(Ｆｅ(ＯＨ)2、Ｆｅ(ＯＨ)3)などであってもよい。 The iron-based metal targeted by the corrosion inhibitor or inhibitor of the present invention is a metal containing iron as a main component (the most contained metal; preferably 50% by weight or more), The ratio of iron in the metal is not limited. The iron-based metal is in a chemical form, for example, iron (Fe), iron oxide (FeO, Fe 2 O 3 , Fe 3 O 4 ), iron oxyhydroxide (FeOOH), iron hydroxide (Fe (OH)). 2 or Fe (OH) 3 ).
本発明の腐食防止又は抑制剤が対象とする金属表面は、例えば、ボイラシステム(水/蒸気循環系、給水系、排水系)の金属表面(例えば、ボイラ(本体)、その配管(例えば、給水管、復水管)、ポンプの内面)；ラジエーターのような熱交換器の金属表面；金型の表面などであり得る。 The metal surface targeted by the corrosion inhibitor or inhibitor of the present invention is, for example, a metal surface of a boiler system (water / steam circulation system, water supply system, drainage system) (for example, boiler (main body), its piping (for example, water supply) Pipes, condensate pipes), pump inner surfaces); metal surfaces of heat exchangers such as radiators; mold surfaces and the like.
本発明の腐食防止又は抑制剤は、揮発性アミンに加えて、ｐＨを上昇させるためのアルカリを含有してもよい。例えば、アルカリ剤としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、リン酸カリウム等が使用できる。
水酸化ナトリウム及び水酸化カリウムについては、単独成分として５％以上含有しているものが毒物及び劇物取締法による規制対象に該当するので、本発明の腐食防止又は抑制剤中の含有量は５％未満であることが好ましい。
水酸化ナトリウム及び水酸化カリウム以外のアルカリの含有量は、例えば０％〜９９％である。
The corrosion inhibitor or inhibitor of the present invention may contain an alkali for increasing the pH in addition to the volatile amine. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, etc. can be used as the alkaline agent.
Regarding sodium hydroxide and potassium hydroxide, those containing 5% or more as a single component fall under the scope of regulation by the Poisonous and Deleterious Substances Control Law, so the content in the corrosion inhibitor or inhibitor of the present invention is 5 It is preferable that it is less than%.
The content of alkali other than sodium hydroxide and potassium hydroxide is, for example, 0% to 99%.
本発明の腐食防止又は抑制剤には、腐食防止又は抑制効果を増強するために、その他の腐食防止又は抑制成分、その他アミン、スケール分散成分等が更に配合されていてもよい。
一般的なその他の腐食防止又は抑制成分としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、リン酸水素２カリウム、グルコン酸及びその塩、酒石酸及びその塩、クエン酸及びその塩、モリブデン酸及びその塩、ベンゾトリアゾール等を指す。
その他の腐食防止又は抑制成分(又はその他のアミン)としては、皮膜性アミンが挙げられる。皮膜性アミンは、炭素数１０〜２４までの飽和又は不飽和の直鎖脂肪族アミン化合物であり、例えば、オクタデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ヘプタデシルアミン、ノナデシルアミン、エイコシルアミン、ドコシルアミンなどである。
In order to enhance the corrosion prevention or inhibition effect, the corrosion prevention or inhibition agent of the present invention may further contain other corrosion prevention or inhibition components, other amines, scale dispersion components and the like.
Examples of other general corrosion preventing or inhibiting components include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, dipotassium hydrogen phosphate, gluconic acid and its salt, tartaric acid and its salt, Citric acid and its salt, molybdic acid and its salt, benzotriazole and the like.
Other corrosion inhibiting or inhibiting components (or other amines) include film-forming amines. The film-forming amine is a saturated or unsaturated linear aliphatic amine compound having 10 to 24 carbon atoms, such as octadecylamine, dodecylamine, tridecylamine, tetradecylamine, heptadecylamine, nonadecylamine, eicosyl. Amines, docosylamines and the like.
その他の腐食防止又は抑制成分の系内の濃度と、鉄系金属の腐食防止又は抑制剤の系内の濃度との存在比は、例えば、１：１０００〜１０００：１の比率で存在し得る。
また、一般的なスケール分散成分としては、ＥＤＴＡといったキレート剤、マレイン酸とその塩、ポリアクリル酸とその塩、ホスホン酸とその塩といった高分子化合物を指す。
スケール分散成分の系内の濃度と、鉄系金属の腐食防止又は抑制剤の系内の濃度との存在比は、例えば、１：１０００〜１０００：１の比率で存在し得る。
The abundance ratio between the concentration of the other corrosion preventing or inhibiting component in the system and the concentration of the iron metal corrosion preventing or inhibiting agent in the system may be, for example, 1: 1000 to 1000: 1.
Moreover, as a general scale dispersion component, it refers to a high molecular compound such as a chelating agent such as EDTA, maleic acid and a salt thereof, polyacrylic acid and a salt thereof, and phosphonic acid and a salt thereof.
The abundance ratio between the concentration of the scale dispersion component in the system and the concentration of the iron-based metal corrosion inhibitor or inhibitor in the system may be, for example, a ratio of 1: 1000 to 1000: 1.
本発明の腐食防止又は抑制剤は、保護(すなわち、腐食を防止又は抑制)しようとする鉄系金属表面と接触する水性媒体(例えば、水又は水蒸気)中に混入させて用いてもよいし、保護対象の鉄系金属(表面)を本発明の腐食防止又は抑制剤中に浸漬させるように用いてもよい。また、ハケやスプレー等による塗布(又は噴霧)で使用してもよい。
理論によって本発明が制限されることは意図していないが、本発明の腐食防止又は抑制剤は、その成分たる揮発性アミンの一部(炭素数が多いもの、例えば５や６のもの)が、鉄系金属表面で皮膜を形成することで該表面と水との接触を防止することによっても、腐食防止又は抑制効果を奏し得る。
The corrosion inhibitor or inhibitor of the present invention may be used by being mixed in an aqueous medium (for example, water or water vapor) in contact with the iron-based metal surface to be protected (that is, preventing or suppressing corrosion) The iron-based metal (surface) to be protected may be used so as to be immersed in the corrosion inhibitor or inhibitor of the present invention. Moreover, you may use by application | coating (or spraying) by a brush or spray.
Although it is not intended that the present invention be limited by theory, the corrosion inhibitor or inhibitor of the present invention contains a part of the component volatile amine (having a large number of carbon atoms, for example, having 5 or 6). Further, by preventing the contact between the surface and water by forming a film on the surface of the iron-based metal, the corrosion prevention or suppression effect can be obtained.
本発明の腐食防止又は抑制剤は、原液で使用してもよいし、倍率を問わず希釈して使用してもよい。
例えば、本発明の腐食防止又は抑制剤は、復水(凝縮水)中のｐＨが６．０〜１１．０、好ましくは７．０〜１０．５、より好ましくは８.０〜１０.５となるように、給水、ボイラ水又は蒸気中に注入され得る。
給水又はボイラ水中への注入時には、ヘキシルアミン及び他の揮発性アミンは、遊離アミン及び塩のいずれの形態であってもよいが、蒸気中への注入時には、遊離アミンの形態が好ましい。
The corrosion inhibitor or inhibitor of the present invention may be used in a stock solution or may be used after diluting regardless of the magnification.
For example, the corrosion inhibitor or inhibitor of the present invention has a pH in condensate (condensed water) of 6.0 to 11.0, preferably 7.0 to 10.5, more preferably 8.0 to 10.5. Can be injected into feed water, boiler water or steam.
When injected into feed water or boiler water, hexylamine and other volatile amines may be in the form of free amine or salt, but when injected into steam, the form of free amine is preferred.
本発明の腐食防止又は抑制剤は、各揮発性アミン及び任意に水を当該分野において公知の方法により混合することで製造することができる。 The corrosion inhibitor or inhibitor of the present invention can be produced by mixing each volatile amine and optionally water by methods known in the art.
本発明の鉄系金属の腐食防止又は抑制方法は、上記の腐食防止又は抑制剤を保護対象の鉄系金属に接する環境中に存在する水及び/又は水蒸気中に混入させることを特徴とする。
保護対象の鉄系金属に接する環境は、Ｈ2Ｏが水(液体状態)で存在する領域及び水蒸気(気体状態)で存在する領域を含んでなる(但し、両領域は該環境中で固定されているとは限らない)。環境は、例えば、ボイラシステムのボイラ及びその配管系(並びに存在する場合には、ポンプ及び/又は排気(排水)装置)や保管倉庫(室)の内部環境であり得る。
The method for preventing or suppressing corrosion of an iron-based metal according to the present invention is characterized in that the above-described corrosion prevention or inhibitor is mixed into water and / or water vapor existing in an environment in contact with the iron-based metal to be protected.
The environment in contact with the iron-based metal to be protected includes a region where H 2 O exists in water (liquid state) and a region where water vapor (gas state) exists (however, both regions are fixed in the environment). Not necessarily). The environment can be, for example, the internal environment of a boiler of a boiler system and its piping system (and pumps and / or exhaust (drainage) devices, if present) and storage warehouses (rooms).
保護対象の鉄系金属表面は、例えば、ボイラシステムの鉄系金属表面(例えば、ボイラ本体及び/又は配管の内面)であり得、この場合、腐食抑制又は防止剤は、ボイラシステムの水系中(給水中、ボイラ水中及び/又は復水中)及び/又は水蒸気系中に注入することができる。
本発明の腐食防止又は抑制方法は、その他の腐食防止又は抑制方法(例えば、脱酸素剤や皮膜性アミンを用いる方法)と併用されてもよい。
The iron-based metal surface to be protected can be, for example, the iron-based metal surface of the boiler system (e.g., the inner surface of the boiler body and / or piping), in which case the corrosion inhibitor or inhibitor is in the water system of the boiler system ( It can be injected into feed water, boiler water and / or condensate) and / or into a steam system.
The corrosion prevention or inhibition method of the present invention may be used in combination with other corrosion prevention or inhibition methods (for example, a method using an oxygen scavenger or a film-forming amine).
以下、理解を容易にするため、本発明の内容を実施例に基づいて具体的に説明するが、本発明はこれらに何ら制限されるものではない。 Hereinafter, for easy understanding, the content of the present invention will be specifically described based on examples, but the present invention is not limited thereto.
蒸気・復水系への腐食防止又は抑制剤の防食効果の評価として、腐食防止又は抑制剤を蒸気内で総アミン濃度が２０ｍｇ/Ｌになるように蒸気・復水系に直接注入し、注入箇所から５０ｍ、１００m及び２００ｍ先における気相部、喫水部及び液相部での腐食防止又は抑制効果を、鉄系金属試験片による腐食の度合いによって判定した。
蒸気・復水系の気相部、喫水部及び液相部を安定して評価するため、図１に示すドレンポット試験器を用いた。ドレンポット試験器は、蒸気が試験器内に流入・滞留することで冷却されて凝縮水となり、凝縮水が一定の水位に達すると出口側のスチームトラップが開放されて凝縮水が排出され、試験器内が常時一定の水位を保つことが出来る仕組みになっている(同一出願人の同日付けの特許出願：特願２０１１−２４０３６４(整理番号ＰＮＧ−１４６０５)を参照)。この仕組みにより再現された気相部、喫水部及び液相部の位置に試験片を設置した。試験片として、低炭素鋼のＪＩＳ Ｇ ３１４１の１種(ＳＰＣＣ)を用いた。試験片の表面状態を全面＃４００研磨仕上げとし、大きさを１ｍｍ×１５ｍｍ×３０ｍｍ、３ｍｍφ×２ヶ所の穴あきとした。
In order to evaluate the corrosion prevention effect of the steam / condensate system or the inhibitor, the corrosion inhibitor or inhibitor is directly injected into the steam / condensate system so that the total amine concentration in the steam is 20 mg / L. The corrosion prevention or suppression effect at the gas phase part, the draft part and the liquid phase part at 50 m, 100 m and 200 m ahead was determined by the degree of corrosion by the iron-based metal specimen.
The drain pot tester shown in FIG. 1 was used in order to stably evaluate the gas phase part, draft part and liquid phase part of the steam / condensate system. The drain pot tester is cooled and becomes condensed water when steam flows in and stays in the tester, and when the condensed water reaches a certain level, the steam trap on the outlet side is opened and the condensed water is discharged. It is a mechanism that can maintain a constant water level in the vessel at all times (see the same applicant's patent application dated on the same date: Japanese Patent Application No. 2011-240364 (reference number PNG-14605)). Test pieces were placed at the positions of the gas phase part, the drafting part and the liquid phase part reproduced by this mechanism. As a test piece, one type of low carbon steel JIS G 3141 (SPCC) was used. The surface state of the test piece was a whole surface # 400 polished finish, and the size was 1 mm × 15 mm × 30 mm, 3 mmφ × 2 holes.
図２のように、腐食防止又は抑制剤の注入箇所から５０ｍ、１００ｍ及び２００ｍのポイントにドレンポット試験器を設置した。ドレンポット試験器内圧力は、薬剤注入箇所から５０ｍのものは１.３ＭＰａ、１００ｍのものは１.０ＭＰａ、２００ｍのものは０.５ＭＰａである。
試験片を蒸気及び凝縮水に接触させ、７日間経過した後に試験片を取り出し、試験後の腐食の度合いを目視により観察した。腐食の度合いの評価基準は、試験片の腐食が全く確認できない場合は○、試験片の表面積の1〜２割程度の腐食が確認された場合は△、試験片の表面積の２割以上腐食が確認された場合は×とした。
As shown in FIG. 2, drain pot testers were installed at points of 50 m, 100 m, and 200 m from the locations where corrosion prevention or inhibitor was injected. The internal pressure of the drain pot tester is 1.3 MPa for 50 m from the injection site, 1.0 MPa for 100 m, and 0.5 MPa for 200 m.
The test piece was brought into contact with steam and condensed water. After 7 days, the test piece was taken out, and the degree of corrosion after the test was visually observed. The evaluation criteria for the degree of corrosion are ○ when the corrosion of the test piece cannot be confirmed at all, △ when the corrosion of about 10 to 20% of the surface area of the test piece is confirmed, and corrosion of 20% or more of the surface area of the test piece. When confirmed, it was set as x.
(実施例１)
ヘキシルアミン(気液分配比１０.０)と、他の揮発性アミンとして２-アミノ-２-メチル-１-プロパノール(気液分配比０.６)及びジエチルアミノエタノール(気液分配比４.０)とを２.５：６２.５：３５.０の割合で混合したものを実施例１の腐食防止又は抑制剤とした。
薬剤注入部位から５０ｍ、１００ｍ及び２００ｍ地点での試験片の腐食度合いの判定結果を表１に示した。
(Example 1)
Hexylamine (gas-liquid partition ratio 10.0) and other volatile amines 2-amino-2-methyl-1-propanol (gas-liquid partition ratio 0.6) and diethylaminoethanol (gas-liquid partition ratio 4.0) ) In a ratio of 2.5: 62.5: 35.0 was used as the corrosion inhibitor or inhibitor of Example 1.
Table 1 shows the determination results of the degree of corrosion of the test pieces at 50 m, 100 m, and 200 m from the drug injection site.
(実施例２)
ヘキシルアミンと、モルホリン(気液分配比１.１)及びジエチルアミノエタノールとを２.５：６２.５：３５.０の割合で混合したものを実施例２の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Example 2)
A mixture of hexylamine, morpholine (gas-liquid distribution ratio 1.1) and diethylaminoethanol in a ratio of 2.5: 62.5: 35.0 was used as the corrosion inhibitor or inhibitor of Example 2. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(実施例３)
ヘキシルアミンと、２-アミノ-２-メチル-１-プロパノール、モルホリン及びジエチルアミノエタノールとを１．０：３３.０：３３.０：３３.０の割合で混合したものを実施例３の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
Example 3
Corrosion prevention of Example 3 was prepared by mixing hexylamine with 2-amino-2-methyl-1-propanol, morpholine and diethylaminoethanol in a ratio of 1.0: 33.0: 33.0: 33.0. Or it was set as the inhibitor. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(実施例４)
ヘキシルアミンと２-アミノ-２-メチル-１-プロパノールとを１０.０：９０.０の割合で混合したものを実施例４の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
Example 4
A mixture obtained by mixing hexylamine and 2-amino-2-methyl-1-propanol at a ratio of 10.0: 90.0 was used as the corrosion inhibitor or inhibitor of Example 4. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(比較例１)
２-アミノ-２-メチル-１-プロパノールとジエチルアミノエタノールとを６２.５：３７.５の割合で混合したものを比較例１の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Comparative Example 1)
A mixture of 2-amino-2-methyl-1-propanol and diethylaminoethanol in a ratio of 62.5: 37.5 was used as the corrosion inhibitor or inhibitor of Comparative Example 1. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(比較例２)
モルホリンとジエチルアミノエタノールとを６２.５：３７.５の割合で混合したものを比較例２の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Comparative Example 2)
A mixture obtained by mixing morpholine and diethylaminoethanol in a ratio of 62.5: 37.5 was used as the corrosion inhibitor or inhibitor of Comparative Example 2. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(比較例３)
２-アミノ-２-メチル-１-プロパノール、モルホリン及びジエチルアミノエタノールを３４.０：３３.０：３３.０の割合で混合したものを比較例３の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Comparative Example 3)
A mixture of 2-amino-2-methyl-1-propanol, morpholine and diethylaminoethanol in a ratio of 34.0: 33.0: 33.0 was used as the corrosion inhibitor or inhibitor of Comparative Example 3. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(比較例４)
２-アミノ-２-メチル-１-プロパノールのみからなるものを比較例４の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Comparative Example 4)
The one consisting only of 2-amino-2-methyl-1-propanol was used as the corrosion inhibitor or inhibitor of Comparative Example 4. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
(比較例５)
アンモニア(気液分配比７.９)と２-アミノ-２-メチル-１-プロパノールとを１０.０：９０.０の割合で混合したものを比較例５の腐食防止又は抑制剤とした。実施例１と同様にして試験片の腐食度合いを判定し、その結果を表１に示した。
(Comparative Example 5)
A mixture obtained by mixing ammonia (gas-liquid distribution ratio 7.9) and 2-amino-2-methyl-1-propanol at a ratio of 10.0: 90.0 was used as the corrosion inhibitor or inhibitor of Comparative Example 5. The degree of corrosion of the test piece was determined in the same manner as in Example 1, and the results are shown in Table 1.
これらの結果から、ヘキシルアミンと気液分配比が１０未満の他の揮発性アミンとを配合した腐食防止又は抑制剤は、注入部位から遠位でも、液相部、気相部及び喫水部のいずれにも腐食(肌荒れ)が確認されなかったことから、本発明の腐食防止又は抑制剤は、ヘキシルアミンを含まない複数の揮発性アミンからなる腐食防止又は抑制剤と比較して、格別優れた腐食防止又は抑制効果を奏し、腐食防止又は抑制剤として高い信頼性を有することが確認できた。 From these results, the corrosion inhibitor or inhibitor containing hexylamine and other volatile amines having a gas-liquid distribution ratio of less than 10 can be used in the liquid phase part, the gas phase part, and the drafting part even at a position remote from the injection site. Since no corrosion (rough skin) was confirmed in any of the above, the corrosion inhibitor or inhibitor of the present invention was exceptionally superior compared to a corrosion inhibitor or inhibitor composed of a plurality of volatile amines not containing hexylamine. It was confirmed that the corrosion prevention or suppression effect was exhibited and that the corrosion prevention or inhibitor was highly reliable.
本発明は、鉄系金属に対する腐食防止又は抑制効果を得ることができるため、腐食が進行する条件に置かれた鉄系金属、つまり水及び酸素の両方の存在する条件下に置かれた鉄系金属に対して腐食の進行を防止又は抑制することが出来る。鉄系金属としては、例えば、鉄塊、ボイラ、配管、金型などのことである。 Since the present invention can obtain an effect of preventing or suppressing corrosion of ferrous metals, the ferrous metals placed under conditions where corrosion progresses, that is, ferrous metals placed under conditions where both water and oxygen exist. It is possible to prevent or suppress the progress of corrosion on the metal. Examples of the iron-based metal include iron blocks, boilers, piping, and molds.
１０ 蒸気の流れ
１１ フランジ部
１２ フランジ部
１３ フランジ部
１４ フランジ部
１５ 試験片取付け用治具
１６ 試験片(気相部)
１７ 試験片(喫水部)
１８ 試験片(液相部)
１９ ドレンポット本体
２０ ドレンポット内部での液面位置
２１ スチームトラップ
２２ ボイラ
２３ 蒸気ヘッダー
２４ 薬剤タンク
２５ 薬剤注入口から５０ｍの距離にあるドレンポット
２６ 薬剤注入口から１００ｍの距離にあるドレンポット
２７ 薬剤注入口から２００ｍの距離にあるドレンポット
２８ 蒸気の流れ
DESCRIPTION OF SYMBOLS 10 Steam flow 11 Flange part 12 Flange part 13 Flange part 14 Flange part 15 Test piece attachment jig 16 Test piece (gas phase part)
17 Test piece (draft)
18 Test piece (liquid phase part)
19 Drain pot body 20 Liquid level position inside the drain pot 21 Steam trap 22 Boiler 23 Steam header 24 Drug tank 25 Drain pot 26 at a distance of 50 m from the chemical injection port Drain pot 27 at a distance of 100 m from the chemical injection port Drain pot 28 at a distance of 200m from the inlet
Claims (10)
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| JP2015124392A (en) * | 2013-12-25 | 2015-07-06 | 住鉱潤滑剤株式会社 | Antirust composition |
| JP2017154049A (en) * | 2016-02-29 | 2017-09-07 | 栗田工業株式会社 | Boiler-water water treatment method |
| CN111334802A (en) * | 2020-04-09 | 2020-06-26 | 苏州热工研究院有限公司 | Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown |
| WO2022054745A1 (en) * | 2020-09-11 | 2022-03-17 | 理研香料ホールディングス株式会社 | Anti-rust deodorizing agent solution |
| CN114427096A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Compound corrosion inhibitor suitable for storage tank gas phase area corrosion medium and preparation method thereof |
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| JP2015124392A (en) * | 2013-12-25 | 2015-07-06 | 住鉱潤滑剤株式会社 | Antirust composition |
| JP2017154049A (en) * | 2016-02-29 | 2017-09-07 | 栗田工業株式会社 | Boiler-water water treatment method |
| CN111334802A (en) * | 2020-04-09 | 2020-06-26 | 苏州热工研究院有限公司 | Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown |
| CN111334802B (en) * | 2020-04-09 | 2022-05-24 | 苏州热工研究院有限公司 | Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown |
| WO2022054745A1 (en) * | 2020-09-11 | 2022-03-17 | 理研香料ホールディングス株式会社 | Anti-rust deodorizing agent solution |
| CN114427096A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Compound corrosion inhibitor suitable for storage tank gas phase area corrosion medium and preparation method thereof |
| CN114427096B (en) * | 2020-10-10 | 2024-02-09 | 中国石油化工股份有限公司 | Compound corrosion inhibitor applicable to storage tank gas phase area corrosive medium and preparation method thereof |
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