US20230064911A1 - Substituted Carboxamide Corrosion Inhibitor Compounds - Google Patents
Substituted Carboxamide Corrosion Inhibitor Compounds Download PDFInfo
- Publication number
- US20230064911A1 US20230064911A1 US17/797,778 US202017797778A US2023064911A1 US 20230064911 A1 US20230064911 A1 US 20230064911A1 US 202017797778 A US202017797778 A US 202017797778A US 2023064911 A1 US2023064911 A1 US 2023064911A1
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- US
- United States
- Prior art keywords
- group
- corrosion inhibitor
- substituted
- heteroatom
- alkenyl group
- Prior art date
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- Pending
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 154
- 230000007797 corrosion Effects 0.000 title claims abstract description 154
- 239000003112 inhibitor Substances 0.000 title claims abstract description 114
- 150000001875 compounds Chemical class 0.000 title claims abstract description 84
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 60
- 150000003857 carboxamides Chemical class 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 125000003342 alkenyl group Chemical group 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 125000005842 heteroatom Chemical group 0.000 claims description 32
- 241001061127 Thione Species 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 24
- 125000000623 heterocyclic group Chemical group 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000000468 ketone group Chemical group 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002576 ketones Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003849 aromatic solvent Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 41
- 239000000203 mixture Substances 0.000 description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 26
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 230000005764 inhibitory process Effects 0.000 description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- 235000021360 Myristic acid Nutrition 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- -1 tall oil fatty acid Chemical class 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 241001311547 Patina Species 0.000 description 1
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 229940098779 methanesulfonic acid Drugs 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
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- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
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Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/02—Surface sealing or packing
- E21B33/03—Well heads; Setting-up thereof
-
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
- E21B41/02—Equipment or details not covered by groups E21B15/00 - E21B40/00 in situ inhibition of corrosion in boreholes or wells
Definitions
- Corrosion is one of the most problematic challenges in the production of oil and gas.
- a common contributor to corrosion is acidic fluids.
- Acidic fluids are present in a multitude of operations in the oil and gas industry. In operations using acidic well fluids, metal surfaces of equipment such as piping, tubing, pumps, blending equipment, and umbilical lines may be exposed to the acidic fluid.
- the acidic fluids may include one or more of a variety of acids, such as hydrochloric acid, acetic acid, formic acid, hydrofluoric acid, or any combination of such acids.
- many fluids used in the oil and gas industry may include a water source that may incidentally contain certain amounts of acid, which, in turn, may cause the fluid to be at least slightly acidic. Even weakly acidic fluids may be problematic in that they may cause corrosion of metals. Corrosion may occur anywhere in a well production system or pipeline system.
- Examples of common types of corrosion include, but are not limited to, the rusting of metal, the dissolution of metal in an acidic solution, and patina development on the surface of a metal.
- the expense of replacing corrosion damaged equipment is high. While the rate at which corrosion will occur depends on a number of factors such as metallurgy, chemical nature of the corrodent, salinity, pH, temperature, etc., some sort of corrosion almost inevitably occurs.
- One way to mitigate this problem includes using corrosion inhibitors in the hydrocarbon production system.
- FIG. 1 illustrates a well production system, according to some embodiments.
- FIG. 2 demonstrates a comparison of inhibited corrosion rates from autoclave tests at 250° F. (121° C.), according to some embodiments.
- FIG. 3 depicts Kettle test results for synthesized carboxamides, according to some embodiments.
- FIG. 4 depicts Kettle test results for synthesized carboxamides with acetic acid, according to some embodiments.
- the present disclosure relates to inhibiting the corrosion of metal surfaces and, more particularly, to the use of substituted carboxamides as a corrosion inhibitor that is effective in oil and gas production.
- the methods, compositions and systems disclosed herein comprise single compounds that may effectively function as corrosion inhibitors.
- the corrosion inhibitor compounds may coat metal surfaces in acidic environments, thereby protecting said surfaces from corroding. This may be advantageous as the minimum effective concentration of the substituted carboxamide present in the corrosion inhibitor compounds may be lower than those currently used in industry. Additionally, the substituted carboxamide may be stable at higher temperatures than those currently used.
- a corrosion inhibitor compound comprising a substituted carboxamide may come into contact with metal surfaces susceptible to corrosion, alone or in combination with other fluids, such as treatment fluids or produced fluids.
- the corrosion inhibitor compound comprising a substituted carboxamide may be prepared and then introduced into a wellbore such that corrosion of metal surfaces (e.g., at surface, the wellhead, or downhole) that come into contact with the fluid may be reduced.
- the corrosion inhibitor compound comprising a substituted carboxamide may be added to produced fluids, either downhole or at the surface, such that corrosion of metal surfaces that come into contact with the produced fluids may be reduced.
- the metals that may be protected include, but are not limited to, steel grade N-80, J-55, P-110, QT800, HS80, and other common oilfield alloys, such as 13Cr, 25Cr, Incoloy 825, and 316L.
- the corrosion inhibitor compounds disclosed herein may comprise an aqueous component.
- the corrosion inhibitor compounds may also be used alone, or with other fluids, including, for example, with fluids that may further comprise an acid.
- the corrosion inhibitor compounds may coat a metal surface in any suitable manner.
- the metal surfaces that may be disposed downhole may be coated with the corrosion inhibitor before the metal surface is disposed downhole.
- the coating of the metal surface may be achieved because the substituted carboxamide is a surfactant and behaves accordingly.
- the substituted carboxamide may form a monolayer at interfaces that may facilitate a lower energy state.
- Hydrophilic or more polar functional groups, such as amides and thiones may be attracted to and may be adsorbed onto the surface of the metal.
- the adsorption of organic inhibitors on the metal surface may be include pi-bond orbital adsorption, electrostatic adsorption, chemisorption, or combinations thereof.
- Suitable substituted carboxamides may be prepared by any of a variety of suitable techniques.
- a substituted carboxamide may be synthesized by reacting equimolar amounts of a substituted or unsubstituted thiourea and a polyalkylene polyamine which may form a primary amine or a secondary amine.
- the formed primary amine or secondary amine may be any substituted amine in which at least one substituent is terminated by a five membered heterocyclic ring having at least one thione group.
- the substituted carboxamide may be synthesized by reacting equimolar amount of substituted or unsubstituted urea and a polyalkylene polyamine.
- One of ordinary skill in the art, along with the present disclosure, may be able to select the appropriate reactants for a given application.
- a substituted carboxamide may be formed by reacting the substituted amine with a fatty acid.
- the substituted amine may be a primary amine or a secondary amine wherein at least one substituent may be terminated by a five-membered heterocyclic ring and wherein at least one pendant group may comprise a ketone group or a thione group.
- the heterocyclic atoms in the five-membered ring may include at least one nitrogen atom.
- Any suitable fatty acid may be used, including, but not limited to, carbonic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, tall oil fatty acid, the like, and/or any combination thereof.
- the amidization reaction may occur at a temperature of about 150° C. to about 200° C. and under atmospheric pressure.
- the produced substituted carboxamide may be any suitable substituted carboxamide capable of providing corrosion inhibition properties fluids.
- a substituted carboxamide wherein at least one substituent is terminated with a heterocyclic five-membered ring with at least one pendent group comprising a ketone group or a thione group may be used.
- Suitable substituted carboxamides may include, but are not limited to, a substituted carboxamide of Formula (1) as follows:
- R 1 may be selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group
- R 2 may be a hydrogen, an alkyl group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof
- R 3 may be an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
- Suitable heteroatoms that may be substituted in R 1 and/or R 2 may include, but are not limited to, nitrogen, oxygen, and sulfur, among others.
- the alkyl, alkenyl, or heteroatom substituted groups of R 1 , R 2 , and R 3 may be the same or different and, in some embodiments, may include 1 carbon atom to 20 carbon atoms.
- the alkyl, alkenyl, or heteroatom substituted groups of R 1 , R 2 , and R 3 may include from 1 to 20 carbon atoms, from 4-15 carbon atoms, or from 5-10 carbon atoms.
- the alkyl, alkenyl, or heteroatom substituted groups of R 1 , R 2 , and R 3 may include from 1 to 6 carbon atoms.
- R 3 may be a chain of 2 to 4 carbon atoms terminated by the five-member heterocyclic rings while R 1 may be a chain of 6 to 20 carbon atoms.
- Suitable substituted carboxamides may depend on the reactants used to create said substituted carboxamide.
- An example of a suitable substituted carboxamide for use as a corrosion inhibitor compounds, shown in Structure (2) below may be formed from reaction of equimolar amounts of thiourea or urea and diethylenetriamine followed by reaction with a carboxylic acid, such as tall oil fatty acid.
- X 1 may be selected from the group consisting of a thione or a ketone, wherein R 1 may be selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- a suitable substituted carboxamide for use as a corrosion inhibitor compound may be formed from reaction of thiourea or urea and tetraethylenepentamine in a 2:1 molar ratio followed by reaction with a carboxylic acid, such as tall oil fatty acid, as shown below in Structure (3):
- X 1 may be individually selected from the group consisting of a thione or a ketone, wherein R 1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Structure (2) may be further reacted with a saturated diacid, an unsaturated diacid, a saturated anhydride, or an unsaturated anhydride to form a substituted carboxamide for use as the corrosion inhibitor compound of Structure (4) as follows:
- X 1 may be individually selected from the group consisting of a thione or a ketone, wherein R 1 is selected from the group consisting of an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Structure (4) may function as a corrosion inhibitor, wherein the distance between the two five-membered rings may be controlled by varying R 1 . In some embodiments as R 1 gets longer or shorter some properties may be affected, such as solubility, viscosity, and melting point.
- Structure (2) or Structure (3) may be further reacted with acids that include, but are not limited to, acrylic acid, acetic acid, thioglycolic acid, glycolic acid, methane sulfonic acid, phosphonic acid, or combinations thereof, to form corrosion inhibitor compounds comprising at least one acrylated five-membered heterocyclic ring wherein at least one pendent group may comprise a ketone group or a thione group, of Structure (5) and Structure (6), respectively, as follows:
- X 1 and X 2 may be individually selected from the group consisting of a thione or a ketone, wherein R 1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein Y is the radical derived from the acid listed above. It may be advantageous to use the above acrylated formulas disclosed herein as they may affect the solubility of the product. For example, depending upon the application, greater or less water or brine solubility may be desired.
- the corrosion inhibitor compounds disclosed herein may be provided in a solvent.
- suitable solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof.
- the solvent may be present in an amount in a range of from about 50 wt. % to about 99.5 wt. %, or about 65 wt. % to about 98 wt. %, or about 80 wt. % to about 90 wt. % based on a total weight of the solvent and the corrosion inhibitor.
- Methods are provided herein for adding one or more corrosion inhibitor compounds to a fluid, wherein the fluid may comprise any one or more of water, a gas, a liquid hydrocarbon, and any combination thereof.
- the method may comprise adding to the fluid an effective amount of an embodiment of the corrosion inhibitor compounds to inhibit, retard, reduce, control, delay, and/or the like the formation of corrosion on metal parts and materials.
- the corrosion inhibitor compounds, and methods of use thereof, as disclosed herein may be introduced into a fluid comprising one or more of water, a gas, a liquid hydrocarbon, or any combination thereof.
- the gas may in some embodiments include gaseous hydrocarbon, though the gas need not necessarily include hydrocarbon.
- the corrosion inhibitor compound may be introduced into the fluid through a conduit or an injection point.
- one or more corrosion inhibitor compounds may be introduced into a wellhead, a wellbore, a subterranean formation, a conduit, a vessel, and the like and may contact and/or be introduced into a fluid residing therein.
- the wellhead, wellbore, subterranean formation, conduit, vessel, or the like may be in a deepwater environment.
- the corrosion inhibitor compounds may be introduced into the deepwater environment by way of an umbilical.
- the fluid may be flowing, or it may be substantially stationary.
- the fluid may contact metal surfaces. By introduction of the corrosion inhibitor compound into the fluid, corrosion of the metal surface may be inhibited.
- the fluid may be within a vessel, or within a conduit (e.g., a conduit that may transport the fluid), or within a subterranean formation, or within a wellbore penetrating a portion of the subterranean formation, and/or within a wellhead of a wellbore.
- conduits include, but are not limited to, pipelines, production piping, subsea tubulars, process equipment, and the like as used in industrial settings and/or as used in the production of oil and/or gas from a subterranean formation, and the like.
- the conduit may in certain embodiments penetrate at least a portion of a subterranean formation, as in the case of an oil and/or gas well.
- the wellhead may be in a deepwater environment.
- the conduit may be a wellhead, a wellbore, or may be located within a wellbore penetrating at least a portion of a subterranean formation.
- the oil and/or gas well may be a subsea well (e.g., with the subterranean formation being located below the sea floor), or it may be a surface well (e.g., with the subterranean formation being located belowground).
- the subsea well may be in a deepwater environment.
- the corrosion inhibitor compounds of the present disclosure initially may be incorporated into a composition prior to being introduced into the fluid.
- the composition may be any suitable composition in which the corrosion inhibitor compound may be included.
- the composition may include a solvent for the corrosion inhibitor compound.
- Suitable solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof.
- the corrosion inhibitor compounds may be introduced into a fluid in any suitable amount for corrosion inhibition.
- the corrosion inhibitor compounds of the present disclosure may be used as low dosage corrosion inhibitors such that an effective concentration of actives in one or more corrosion inhibitor compounds for inhibiting, retarding, mitigating, reducing, controlling, and/or delaying corrosion may from about 2 ppm to about 1,000 ppm by volume.
- the concentrations of actives may be from about 2 ppm to about 1,000 ppm, about 2.25 ppm to about 900 ppm, about 2.5 ppm to about 800 ppm, about 2.75 ppm to about 700 ppm, about 3 ppm to about 600 ppm, about 3.25 ppm to about 500 ppm, about 3.5 ppm to about 400 ppm, about 3.75 ppm to about 300 ppm, about 4 ppm to about 200 ppm, about 4.5 ppm to about 100 ppm, or about 5 ppm to about 50 ppm by volume.
- the corrosion inhibitor compounds may be suitable in applications with temperatures up to 350° F. (177° C.) under pressures of about 1 atm to about 300 atms.
- the corrosion inhibitor compounds may be introduced into a wellhead of a wellbore penetrating at least a portion of the subterranean formation, a wellbore, a subterranean formation, a vessel, and/or a conduit (and/or into a fluid within any of the foregoing) using any method or equipment known in the art.
- a corrosion inhibitor compound of the present disclosure may be injected into a portion of a subterranean formation using an annular space or capillary injection system to continuously introduce the corrosion inhibitor compound into the formation.
- the capillary injection may include an umbilical with the wellhead in a deepwater environment.
- a composition comprising a corrosion inhibitor compound of the present disclosure may be circulated in the wellbore using the same types of pumping systems and equipment at the surface that may be used to introduce fluids or additives into a wellbore penetrating at least a portion of the subterranean formation.
- this disclosure describes methods, systems, and compositions that may use a substituted carboxamide as corrosion inhibitor compounds.
- the methods, systems, and compositions may include any of the following statements:
- a method of inhibiting corrosion of a metal surface may comprise contacting the metal surface with a corrosion inhibitor compound comprising a substituted carboxamide.
- Statement 2 The method of statement 1, further comprising coating the metal surface with the corrosion inhibitor compound.
- Statement 3 The method of statement 1 or 2, further comprising introducing the corrosion inhibitor compound into a wellbore, wherein the metal surface is disposed in the wellbore.
- the substituted carboxamide comprises the molecular formula: R 1 C(O)NR 2 R 3 , wherein R 1 is selected from the group consisting of a hydrogen, an alkyl group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group; wherein R 2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof; and wherein R 3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
- X 1 is selected from the group consisting of a thione or a ketone, and wherein R 1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- X 1 is individually selected from the group consisting of a thione or a ketone; and wherein R 1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- X 1 is individually selected from the group consisting of a thione or a ketone, and wherein R 1 is selected from the group consisting of an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Statement 10 The method of statement 3, wherein the introducing the corrosion inhibitor compound into the wellbore comprises pumping the corrosion inhibitor compound from a fluid supply, through a production tubing, and into the wellbore, and mixing the corrosion inhibitor compound with a produced fluid.
- Statement 11 The method of statement 10, further comprising transporting the corrosion inhibitor compound mixed with the produced fluid to a surface of the wellbore, and coating at least one metal surface in which the corrosion inhibitor compound mixed with the produced fluid contacts.
- Statement 16 The method of statement 9 wherein the solvent is present in an amount of about 50 wt % to about 99.5 wt % based on the total weight of the solvent and the corrosion inhibitor.
- a corrosion inhibitor may comprise: a solvent package; and a corrosion inhibitor compound comprising a substituted carboxamide having the formula: R 1 C(O)NR 2 R 3 , wherein R 1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein R 2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, and wherein R 3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any
- Statement 18 The method of statement 17 wherein the solvent package comprises solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, butyl cellulose, aromatic solvents, and combinations thereof.
- solvent package comprises solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, butyl cellulose, aromatic solvents, and combinations thereof.
- a system for introducing a corrosion inhibitor into a wellbore may comprise: a fluid supply containing the corrosion inhibitor, wherein the corrosion inhibitor comprises a corrosion inhibitor compound and a solvent package, wherein the corrosion inhibitor compound comprises a substituted carboxamide; and a tubular in a wellbore in a subterranean formation, wherein the tubular is in fluid communication with the corrosion inhibitor supply.
- FIG. 1 illustrates a well production system.
- An example system 100 for introduction of corrosion inhibitor compounds described herein into a wellbore 118 is shown.
- Well system 100 may comprise a wellbore 118 formed within a formation 104 .
- Wellbore 118 may be a vertical wellbore as illustrated or it may be a horizontal and/or a directional well. While well system 100 may be illustrate as land-based, it should be understood that the present techniques may also be applicable in offshore applications.
- Formation 104 may be comprised of several geological layers and may include one or more hydrocarbon reservoirs.
- well system 100 may include a production tree 106 and a wellhead 112 located at a well site 110 .
- a production tubing 124 may extend from wellhead 112 into wellbore 118 , which may traverse formation 114 .
- the wellbore 118 may be cased with one or more casings 114 .
- Casing 114 may support and maintain the structure of wellbore 118 and prevent wellbore 118 from collapsing. In some embodiments, a portion of the well may not be cased and may be referred to as “open hole.”
- the space between production tubing 124 and casing 126 or wellbore wall 118 may be an annulus 134 .
- Production fluid 138 may enter annulus 134 from formation 114 and then may enter production tubing 124 from annulus 134 .
- Production tubing 124 may carry production fluid 138 uphole to production tree 106 . Production fluid 138 may then be delivered to various surface facilities for processing via a surface pipeline 120 .
- corrosion inhibitor compounds 150 may be introduced into annulus 134 between production tubing 124 and casing 136 . As previously described, corrosion inhibitor compounds 150 may be used alone, or they may be added to produced fluids, treatment fluids, and other additives. Corrosion inhibitor compounds 150 may be introduced into wellbore 118 in any suitable manner. In some embodiments, corrosion inhibitor compounds 150 may be injected into wellbore 118 at wellhead 112 . In an embodiment, corrosion inhibitor compounds 150 may be continuously provided to wellbore 118 . Suitable techniques for introduction of corrosion inhibitor compounds 150 may include, but are not limited to, neat annulus drip, slip stream, capillary string, or batch processes. As illustrated, corrosion inhibitor compounds 150 may be introduced to wellbore at wellhead 112 by way of neat annulus drip.
- Corrosion inhibitor compounds may flow through wellhead 112 and into annulus 134 formed between production tubing 124 and casing 136 . Corrosion inhibitor compounds 150 may fall and/or drip to the bottom of wellbore 118 . At the bottom of wellbore 132 , corrosion inhibitor compounds 150 may mix with the produced fluids 138 . The mixture 142 of corrosion inhibitor compounds 150 and produced fluids 138 may then be pumped through downhole tools 140 and up production tubing 124 .
- the corrosion inhibitor compounds 150 and the produced fluids 138 may continuously be in contact with production tubing 124 , slickline 122 , and downhole tools 140 , in turn which may provide production tubing 124 , slickline 122 , and downhole tools 140 with corrosion resistance.
- This provided corrosion resistance may reduce the corrosion on said metal components of well system 100 and in turn extend the production life of said metal components.
- well system 100 may be used for delivery of corrosion inhibitor compounds 150 into wellbore 118 .
- Corrosion inhibitor compounds 150 may be pumped from fluid supply (not shown) down the interior of production tubing 124 in wellbore 118 .
- Corrosion inhibitor compounds 150 may be allowed to flow down the interior of production tubing 124 .
- Corrosion inhibitor compounds 150 may exit production tubing 124 and mix with produced fluids 138 .
- Fluid 130 comprising a corrosion inhibitor may coat any metal surface in which corrosion inhibitor compounds 150 may contact while being placed downhole.
- corrosion inhibitor compounds 150 that may be mixed with produced fluid 138 may be brought back to the surface and may coat any metal surface in which the mixture fluid 142 may come in contact with.
- the disclosed corrosion inhibitor compounds may also directly or indirectly affect the various downhole equipment and tools that may come into contact with the corrosion inhibitor compounds during operation.
- equipment and tools may include, but are not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, surface-mounted motors and/or pumps, centralizers, turbolizers, scratchers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanical devices, etc.), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc.), control lines (e.g., electrical, fiber optic,
- FIG. 2 demonstrates a comparison of inhibited corrosion rates from autoclave tests at 250° F. (121° C.).
- the synthesized carboxamides tests all contained 10 ppm of actives based on the brine volume.
- the results shown in FIG. 2 illustrate the effectiveness of the synthesized carboxamide corrosion inhibitor compounds as evaluated in a series of autoclave tests.
- Each test contained 1.17 liters of synthetic field brine, 430 ml of kerosene and a single UNS10180 coupon (27.88 cm 2 ).
- the test solutions were deaerated and saturated with CO 2 at a partial pressure of 19.6 psia (135 KPa), stirred with an inline mixer (1,500 rpm) and heated to 250° F. (121° C.).
- the corrosion inhibitor compounds were formulated by adding 1 gram of actives to 10 grams of solvent (9% active). The corrosion inhibitor compounds were then injected into the test solutions at 112 ppm, which equates to 10 ppm of actives. The time for completion of the tests ranged from 20 hours to 23 hours. Upon completion of the tests, the coupons were removed from the autoclaves and cleaned in an inhibited acid bath according to ASTM G1 C.3.5. As shown in FIG. 2 , the synthesized products outperformed two commonly used corrosion inhibitor intermediates and several formulated products that are currently used in the oilfield. Intermediates A and A+C resulted in a corrosion rates of 87.7 mpy and 120 mpy, respectively.
- Formulations Z, Y, and X resulted in corrosion rates of 44 mpy, 151.7 mpy, and 139.9 mpy, respectively.
- the TEPA/Thiourea/Myristic Acid composition resulted in a corrosion rate of 20.2 mpy.
- the DETA/Thiorea/Myristic Acid composition resulted in a corrosion rate of 22.5 mpy.
- the DETA/Thiourea/Lauric Acid composition resulted in a corrosion rate of 27.6 mpy.
- Table 1 The compositions of intermediates A, C, X, Y, and Z in FIG. 2 are shown in Table 1.
- FIG. 3 depicts Kettle test results for unsalted synthesized carboxamides using Structures (2) and (3) as shown above in accordance with ASTM G31—Standard Practice for Laboratory Immersion Corrosion Testing of Metals and ASTM G170—Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory.
- the Kettle tests were continuously purged with anaerobic grade CO 2 , having a partial pressure of 10.8 psia (74 KPa), 800 ml of sea-salt brine, 80 ml of kerosene, heated to 150° F. (66° C.) and stirred with a magnetic stir bar/plate.
- the synthesized carboxamides were dissolved in methanol (5% actives) and injected at 100 ppm (5 ppm actives) and then up to 200 ppm (10 ppm actives), based on the total test volume.
- a Kettle test using a first composition comprising Structure (2) included a mixture of 38.05 g (0.5 mole) of thiourea and 51.6 g (0.5 mole) of diethylenetriamine (DETA). The mixture was charged to a 250-mL glass kettle equipped with a condenser, a stirrer, and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and lauric acid (100.16 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- DETA diethylenetriamine
- a Kettle test using a second composition comprising Structure (2) included a mixture of 38.05 g (0.5 mole) of thiourea and 51.6 g (0.5 mole) of diethylenetriamine (DETA) was charged to a 250-mL glass kettle equipped with a condenser, a stirrer and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and myristic acid (114.2 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- DETA diethylenetriamine
- a Kettle test using a composition comprising Structure (3) included a mixture of 76.1 g (1.0 mole) of thiourea and 94.7 g (0.5 mole) of tetraethylenepentamine (TEPA) was charged to a 250-mL glass kettle equipped with a condenser, a stirrer and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and myristic acid (114.2 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- TEPA tetraethylenepentamine
- the baseline or uninhibited corrosion rate was monitored for 0.85 hours before the corrosion inhibitors were injected at 100 ppm (5 ppm actives).
- 100 ppm (5 ppm actives) the average baseline corrosion rate was reduced from 174 mils per year (“MPY”) to 35, 77 and 4 MPY for the DETA/Thiourea/Lauric, DETA/Thiourea/Myristic and TEPA/Thiourea/Myristic reaction product, as depicted in FIG. 3 . This resulted in inhibition efficiencies of 80, 56 and 97%, respectively.
- the treatment rate was increased to 200 ppm (10 ppm actives total) at the 4 hour mark for the DETA/Thiourea/Lauric and DETA/Thiourea/Myristic tests, which reduced the corrosion rates to 7 MPY (96% inhibition efficiency) and 62 MPY (64% inhibition efficiency), respectively.
- FIG. 4 depicts Kettle test results for synthesized carboxamides salted with acetic acid in accordance with ASTM G31—Standard Practice for Laboratory Immersion Corrosion Testing of Metals and ASTM G170—Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory.
- the synthesized carboxamides were evaluated with Kettle tests run with 810 ml of sea-salt brine, 90 ml of kerosene, and continuously purged with anaerobic grade CO 2 , with a partial pressure of 10.8 psia (74 KPa). The Kettle tests were heated to 150° F.
- Both electrodes were contained in an electrochemical cell, where the potentiostat was used to measure the current flow between the working and reference electrodes.
- the free-corroding potential, or the potential of the metal in the absence of any net current flow, was scanned over range of +/ ⁇ 13 mV at a rate of 0.4 mV/second. It should be noted that free corrosion potential is the absence of a net electrical current that flows to and from a metal's surface. The free corrosion potential is measured through the voltage difference between the immersed metal and the appropriate reference electrode in a given environment.
- the efficiency of a corrosion inhibitor increases with an increase in inhibitor concentration.
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Abstract
A method of inhibiting corrosion of a metal surface may include contacting the metal surface with a corrosion inhibitor compound that includes a substituted carboxamide.
Description
- Corrosion is one of the most problematic challenges in the production of oil and gas. A common contributor to corrosion is acidic fluids. Acidic fluids are present in a multitude of operations in the oil and gas industry. In operations using acidic well fluids, metal surfaces of equipment such as piping, tubing, pumps, blending equipment, and umbilical lines may be exposed to the acidic fluid. The acidic fluids may include one or more of a variety of acids, such as hydrochloric acid, acetic acid, formic acid, hydrofluoric acid, or any combination of such acids. In addition, many fluids used in the oil and gas industry may include a water source that may incidentally contain certain amounts of acid, which, in turn, may cause the fluid to be at least slightly acidic. Even weakly acidic fluids may be problematic in that they may cause corrosion of metals. Corrosion may occur anywhere in a well production system or pipeline system.
- Examples of common types of corrosion include, but are not limited to, the rusting of metal, the dissolution of metal in an acidic solution, and patina development on the surface of a metal. The expense of replacing corrosion damaged equipment is high. While the rate at which corrosion will occur depends on a number of factors such as metallurgy, chemical nature of the corrodent, salinity, pH, temperature, etc., some sort of corrosion almost inevitably occurs. One way to mitigate this problem includes using corrosion inhibitors in the hydrocarbon production system.
- For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:
-
FIG. 1 illustrates a well production system, according to some embodiments. -
FIG. 2 demonstrates a comparison of inhibited corrosion rates from autoclave tests at 250° F. (121° C.), according to some embodiments. -
FIG. 3 depicts Kettle test results for synthesized carboxamides, according to some embodiments. -
FIG. 4 depicts Kettle test results for synthesized carboxamides with acetic acid, according to some embodiments. - The present disclosure relates to inhibiting the corrosion of metal surfaces and, more particularly, to the use of substituted carboxamides as a corrosion inhibitor that is effective in oil and gas production. The methods, compositions and systems disclosed herein comprise single compounds that may effectively function as corrosion inhibitors. The corrosion inhibitor compounds may coat metal surfaces in acidic environments, thereby protecting said surfaces from corroding. This may be advantageous as the minimum effective concentration of the substituted carboxamide present in the corrosion inhibitor compounds may be lower than those currently used in industry. Additionally, the substituted carboxamide may be stable at higher temperatures than those currently used.
- For inhibition of corrosion, a corrosion inhibitor compound comprising a substituted carboxamide may come into contact with metal surfaces susceptible to corrosion, alone or in combination with other fluids, such as treatment fluids or produced fluids. For example, the corrosion inhibitor compound comprising a substituted carboxamide may be prepared and then introduced into a wellbore such that corrosion of metal surfaces (e.g., at surface, the wellhead, or downhole) that come into contact with the fluid may be reduced. Alternatively, the corrosion inhibitor compound comprising a substituted carboxamide may be added to produced fluids, either downhole or at the surface, such that corrosion of metal surfaces that come into contact with the produced fluids may be reduced. The metals that may be protected include, but are not limited to, steel grade N-80, J-55, P-110, QT800, HS80, and other common oilfield alloys, such as 13Cr, 25Cr, Incoloy 825, and 316L. The corrosion inhibitor compounds disclosed herein may comprise an aqueous component. The corrosion inhibitor compounds may also be used alone, or with other fluids, including, for example, with fluids that may further comprise an acid.
- The corrosion inhibitor compounds may coat a metal surface in any suitable manner. In some embodiments, the metal surfaces that may be disposed downhole may be coated with the corrosion inhibitor before the metal surface is disposed downhole. The coating of the metal surface may be achieved because the substituted carboxamide is a surfactant and behaves accordingly. For example, the substituted carboxamide may form a monolayer at interfaces that may facilitate a lower energy state. Hydrophilic or more polar functional groups, such as amides and thiones, may be attracted to and may be adsorbed onto the surface of the metal. The adsorption of organic inhibitors on the metal surface may be include pi-bond orbital adsorption, electrostatic adsorption, chemisorption, or combinations thereof.
- Suitable substituted carboxamides may be prepared by any of a variety of suitable techniques. In some embodiments, a substituted carboxamide may be synthesized by reacting equimolar amounts of a substituted or unsubstituted thiourea and a polyalkylene polyamine which may form a primary amine or a secondary amine. The formed primary amine or secondary amine may be any substituted amine in which at least one substituent is terminated by a five membered heterocyclic ring having at least one thione group. In some embodiments, the substituted carboxamide may be synthesized by reacting equimolar amount of substituted or unsubstituted urea and a polyalkylene polyamine. One of ordinary skill in the art, along with the present disclosure, may be able to select the appropriate reactants for a given application.
- A substituted carboxamide may be formed by reacting the substituted amine with a fatty acid. The substituted amine may be a primary amine or a secondary amine wherein at least one substituent may be terminated by a five-membered heterocyclic ring and wherein at least one pendant group may comprise a ketone group or a thione group. In some embodiments, the heterocyclic atoms in the five-membered ring may include at least one nitrogen atom. Any suitable fatty acid may be used, including, but not limited to, carbonic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, tall oil fatty acid, the like, and/or any combination thereof. The amidization reaction may occur at a temperature of about 150° C. to about 200° C. and under atmospheric pressure.
- The produced substituted carboxamide may be any suitable substituted carboxamide capable of providing corrosion inhibition properties fluids. In some embodiments, a substituted carboxamide wherein at least one substituent is terminated with a heterocyclic five-membered ring with at least one pendent group comprising a ketone group or a thione group may be used. Suitable substituted carboxamides may include, but are not limited to, a substituted carboxamide of Formula (1) as follows:
- wherein R1 may be selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein R2 may be a hydrogen, an alkyl group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, wherein R3 may be an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof. Suitable heteroatoms that may be substituted in R1 and/or R2 may include, but are not limited to, nitrogen, oxygen, and sulfur, among others. The alkyl, alkenyl, or heteroatom substituted groups of R1, R2, and R3 may be the same or different and, in some embodiments, may include 1 carbon atom to 20 carbon atoms. Alternatively, the alkyl, alkenyl, or heteroatom substituted groups of R1, R2, and R3 may include from 1 to 20 carbon atoms, from 4-15 carbon atoms, or from 5-10 carbon atoms. In some embodiments, the alkyl, alkenyl, or heteroatom substituted groups of R1, R2, and R3 may include from 1 to 6 carbon atoms. For example, R3 may be a chain of 2 to 4 carbon atoms terminated by the five-member heterocyclic rings while R1 may be a chain of 6 to 20 carbon atoms.
- Examples of suitable substituted carboxamides may depend on the reactants used to create said substituted carboxamide. An example of a suitable substituted carboxamide for use as a corrosion inhibitor compounds, shown in Structure (2) below may be formed from reaction of equimolar amounts of thiourea or urea and diethylenetriamine followed by reaction with a carboxylic acid, such as tall oil fatty acid.
- wherein X1 may be selected from the group consisting of a thione or a ketone, wherein R1 may be selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Another example of a suitable substituted carboxamide for use as a corrosion inhibitor compound may be formed from reaction of thiourea or urea and tetraethylenepentamine in a 2:1 molar ratio followed by reaction with a carboxylic acid, such as tall oil fatty acid, as shown below in Structure (3):
- wherein X1 may be individually selected from the group consisting of a thione or a ketone, wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- In some embodiments, Structure (2) may be further reacted with a saturated diacid, an unsaturated diacid, a saturated anhydride, or an unsaturated anhydride to form a substituted carboxamide for use as the corrosion inhibitor compound of Structure (4) as follows:
- wherein X1 may be individually selected from the group consisting of a thione or a ketone, wherein R1 is selected from the group consisting of an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group. In some embodiments, Structure (4) may function as a corrosion inhibitor, wherein the distance between the two five-membered rings may be controlled by varying R1. In some embodiments as R1 gets longer or shorter some properties may be affected, such as solubility, viscosity, and melting point. In another embodiment, Structure (2) or Structure (3) may be further reacted with acids that include, but are not limited to, acrylic acid, acetic acid, thioglycolic acid, glycolic acid, methane sulfonic acid, phosphonic acid, or combinations thereof, to form corrosion inhibitor compounds comprising at least one acrylated five-membered heterocyclic ring wherein at least one pendent group may comprise a ketone group or a thione group, of Structure (5) and Structure (6), respectively, as follows:
- wherein X1 and X2 may be individually selected from the group consisting of a thione or a ketone, wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein Y is the radical derived from the acid listed above. It may be advantageous to use the above acrylated formulas disclosed herein as they may affect the solubility of the product. For example, depending upon the application, greater or less water or brine solubility may be desired.
- In some embodiments, the corrosion inhibitor compounds disclosed herein may be provided in a solvent. Suitable solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof. In some embodiments, the solvent may be present in an amount in a range of from about 50 wt. % to about 99.5 wt. %, or about 65 wt. % to about 98 wt. %, or about 80 wt. % to about 90 wt. % based on a total weight of the solvent and the corrosion inhibitor.
- Methods are provided herein for adding one or more corrosion inhibitor compounds to a fluid, wherein the fluid may comprise any one or more of water, a gas, a liquid hydrocarbon, and any combination thereof. In certain embodiments, the method may comprise adding to the fluid an effective amount of an embodiment of the corrosion inhibitor compounds to inhibit, retard, reduce, control, delay, and/or the like the formation of corrosion on metal parts and materials.
- It should be noted that the corrosion inhibitor compounds, and methods of use thereof, as disclosed herein, may be introduced into a fluid comprising one or more of water, a gas, a liquid hydrocarbon, or any combination thereof. Although listed separately from liquid hydrocarbon, the gas may in some embodiments include gaseous hydrocarbon, though the gas need not necessarily include hydrocarbon. In certain embodiments, the corrosion inhibitor compound may be introduced into the fluid through a conduit or an injection point. In certain embodiments, one or more corrosion inhibitor compounds may be introduced into a wellhead, a wellbore, a subterranean formation, a conduit, a vessel, and the like and may contact and/or be introduced into a fluid residing therein. In at least one embodiment, the wellhead, wellbore, subterranean formation, conduit, vessel, or the like may be in a deepwater environment. In at least one embodiment, the corrosion inhibitor compounds may be introduced into the deepwater environment by way of an umbilical. In certain embodiments, the fluid may be flowing, or it may be substantially stationary. In some instances, the fluid may contact metal surfaces. By introduction of the corrosion inhibitor compound into the fluid, corrosion of the metal surface may be inhibited.
- In certain embodiments, the fluid may be within a vessel, or within a conduit (e.g., a conduit that may transport the fluid), or within a subterranean formation, or within a wellbore penetrating a portion of the subterranean formation, and/or within a wellhead of a wellbore. Examples of conduits include, but are not limited to, pipelines, production piping, subsea tubulars, process equipment, and the like as used in industrial settings and/or as used in the production of oil and/or gas from a subterranean formation, and the like. The conduit may in certain embodiments penetrate at least a portion of a subterranean formation, as in the case of an oil and/or gas well. In some embodiments, the wellhead may be in a deepwater environment. In particular embodiments, the conduit may be a wellhead, a wellbore, or may be located within a wellbore penetrating at least a portion of a subterranean formation. The oil and/or gas well may be a subsea well (e.g., with the subterranean formation being located below the sea floor), or it may be a surface well (e.g., with the subterranean formation being located belowground). In some embodiments, the subsea well may be in a deepwater environment.
- In some embodiments, the corrosion inhibitor compounds of the present disclosure initially may be incorporated into a composition prior to being introduced into the fluid. The composition may be any suitable composition in which the corrosion inhibitor compound may be included. For example, the composition may include a solvent for the corrosion inhibitor compound. Suitable solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof.
- In some embodiments, the corrosion inhibitor compounds may be introduced into a fluid in any suitable amount for corrosion inhibition. In various embodiments, the corrosion inhibitor compounds of the present disclosure may be used as low dosage corrosion inhibitors such that an effective concentration of actives in one or more corrosion inhibitor compounds for inhibiting, retarding, mitigating, reducing, controlling, and/or delaying corrosion may from about 2 ppm to about 1,000 ppm by volume. Alternatively, the concentrations of actives may be from about 2 ppm to about 1,000 ppm, about 2.25 ppm to about 900 ppm, about 2.5 ppm to about 800 ppm, about 2.75 ppm to about 700 ppm, about 3 ppm to about 600 ppm, about 3.25 ppm to about 500 ppm, about 3.5 ppm to about 400 ppm, about 3.75 ppm to about 300 ppm, about 4 ppm to about 200 ppm, about 4.5 ppm to about 100 ppm, or about 5 ppm to about 50 ppm by volume. In some embodiments, the corrosion inhibitor compounds may be suitable in applications with temperatures up to 350° F. (177° C.) under pressures of about 1 atm to about 300 atms.
- In certain embodiments, the corrosion inhibitor compounds may be introduced into a wellhead of a wellbore penetrating at least a portion of the subterranean formation, a wellbore, a subterranean formation, a vessel, and/or a conduit (and/or into a fluid within any of the foregoing) using any method or equipment known in the art. In other embodiments, a corrosion inhibitor compound of the present disclosure may be injected into a portion of a subterranean formation using an annular space or capillary injection system to continuously introduce the corrosion inhibitor compound into the formation. In some embodiments, the capillary injection may include an umbilical with the wellhead in a deepwater environment. In certain embodiments, a composition comprising a corrosion inhibitor compound of the present disclosure may be circulated in the wellbore using the same types of pumping systems and equipment at the surface that may be used to introduce fluids or additives into a wellbore penetrating at least a portion of the subterranean formation.
- Accordingly, this disclosure describes methods, systems, and compositions that may use a substituted carboxamide as corrosion inhibitor compounds. The methods, systems, and compositions may include any of the following statements:
-
Statement 1. A method of inhibiting corrosion of a metal surface may comprise contacting the metal surface with a corrosion inhibitor compound comprising a substituted carboxamide. -
Statement 2. The method ofstatement 1, further comprising coating the metal surface with the corrosion inhibitor compound. - Statement 3. The method of
statement -
Statement 4. The method of any of the preceding statements, wherein the substituted carboxamide comprises the molecular formula: R1C(O)NR2R3, wherein R1 is selected from the group consisting of a hydrogen, an alkyl group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group; wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof; and wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof. - Statement 5. The method of any of the preceding statements, wherein the substituted carboxamide comprises the molecular formula:
- wherein X1 is selected from the group consisting of a thione or a ketone, and wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Statement 6. The method of any of the preceding statements, wherein the substituted carboxamide comprises the molecular formula:
- wherein X1 is individually selected from the group consisting of a thione or a ketone; and wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
- Statement 7. The method of any of the preceding statements, wherein the substituted carboxamide comprises the molecular formula:
- wherein X1 is individually selected from the group consisting of a thione or a ketone, and wherein R1 is selected from the group consisting of an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group.
-
Statement 8. The method of any of the preceding statements, wherein the substituted carboxamide is present in the fluid in an amount of from about 10 ppm to about 500 ppm. - Statement 9. The method of any of the preceding statements, wherein the corrosion inhibitor compound is provided in a solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof.
-
Statement 10. The method of statement 3, wherein the introducing the corrosion inhibitor compound into the wellbore comprises pumping the corrosion inhibitor compound from a fluid supply, through a production tubing, and into the wellbore, and mixing the corrosion inhibitor compound with a produced fluid. - Statement 11. The method of
statement 10, further comprising transporting the corrosion inhibitor compound mixed with the produced fluid to a surface of the wellbore, and coating at least one metal surface in which the corrosion inhibitor compound mixed with the produced fluid contacts. -
Statement 12. The method ofstatement 4, wherein R2 is a heteroatom substituted five-membered heterocyclic ring with at least one pendent group comprising a ketone group or a thione group. - Statement 13. The method of
statement 12, wherein the heteroatom substituted five-membered heterocyclic ring comprises nitrogen. -
Statement 14. The method of statement 5, wherein the substituted carboxamide is alkylated. -
Statement 15. The method ofstatement 6, wherein the substituted carboxamide is alkylated. -
Statement 16. The method of statement 9 wherein the solvent is present in an amount of about 50 wt % to about 99.5 wt % based on the total weight of the solvent and the corrosion inhibitor. - Statement 17. A corrosion inhibitor may comprise: a solvent package; and a corrosion inhibitor compound comprising a substituted carboxamide having the formula: R1C(O)NR2R3, wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, and wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
-
Statement 18. The method of statement 17 wherein the solvent package comprises solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, butyl cellulose, aromatic solvents, and combinations thereof. - Statement 19. A system for introducing a corrosion inhibitor into a wellbore may comprise: a fluid supply containing the corrosion inhibitor, wherein the corrosion inhibitor comprises a corrosion inhibitor compound and a solvent package, wherein the corrosion inhibitor compound comprises a substituted carboxamide; and a tubular in a wellbore in a subterranean formation, wherein the tubular is in fluid communication with the corrosion inhibitor supply.
-
Statement 20. A system according to statement 19, wherein the substituted carboxamide has the formula: R1C(O)NR2R3, wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group, wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, and wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof. -
FIG. 1 illustrates a well production system. Anexample system 100 for introduction of corrosion inhibitor compounds described herein into awellbore 118 is shown. Wellsystem 100 may comprise awellbore 118 formed within a formation 104.Wellbore 118 may be a vertical wellbore as illustrated or it may be a horizontal and/or a directional well. Whilewell system 100 may be illustrate as land-based, it should be understood that the present techniques may also be applicable in offshore applications. Formation 104 may be comprised of several geological layers and may include one or more hydrocarbon reservoirs. As illustrated,well system 100 may include aproduction tree 106 and awellhead 112 located at awell site 110. Aproduction tubing 124 may extend fromwellhead 112 intowellbore 118, which may traverseformation 114. - The
wellbore 118 may be cased with one ormore casings 114. Casing 114 may support and maintain the structure ofwellbore 118 and prevent wellbore 118 from collapsing. In some embodiments, a portion of the well may not be cased and may be referred to as “open hole.” The space betweenproduction tubing 124 andcasing 126 orwellbore wall 118 may be anannulus 134.Production fluid 138 may enterannulus 134 fromformation 114 and then may enterproduction tubing 124 fromannulus 134.Production tubing 124 may carryproduction fluid 138 uphole toproduction tree 106.Production fluid 138 may then be delivered to various surface facilities for processing via asurface pipeline 120. - As illustrated, corrosion inhibitor compounds 150 may be introduced into
annulus 134 betweenproduction tubing 124 andcasing 136. As previously described, corrosion inhibitor compounds 150 may be used alone, or they may be added to produced fluids, treatment fluids, and other additives. Corrosion inhibitor compounds 150 may be introduced intowellbore 118 in any suitable manner. In some embodiments, corrosion inhibitor compounds 150 may be injected intowellbore 118 atwellhead 112. In an embodiment, corrosion inhibitor compounds 150 may be continuously provided towellbore 118. Suitable techniques for introduction of corrosion inhibitor compounds 150 may include, but are not limited to, neat annulus drip, slip stream, capillary string, or batch processes. As illustrated, corrosion inhibitor compounds 150 may be introduced to wellbore atwellhead 112 by way of neat annulus drip. Corrosion inhibitor compounds may flow throughwellhead 112 and intoannulus 134 formed betweenproduction tubing 124 andcasing 136. Corrosion inhibitor compounds 150 may fall and/or drip to the bottom ofwellbore 118. At the bottom of wellbore 132, corrosion inhibitor compounds 150 may mix with the producedfluids 138. Themixture 142 of corrosion inhibitor compounds 150 and producedfluids 138 may then be pumped throughdownhole tools 140 and upproduction tubing 124. As themixture 142 of corrosion inhibitor compounds 150 and the producedfluids 138 flow throughproduction tree 106, the corrosion inhibitor compounds 150 and the producedfluids 138 may continuously be in contact withproduction tubing 124,slickline 122, anddownhole tools 140, in turn which may provideproduction tubing 124,slickline 122, anddownhole tools 140 with corrosion resistance. This provided corrosion resistance may reduce the corrosion on said metal components ofwell system 100 and in turn extend the production life of said metal components. - In some embodiments, with continued reference to the
FIG. 1 ,well system 100 may be used for delivery of corrosion inhibitor compounds 150 intowellbore 118. Corrosion inhibitor compounds 150 may be pumped from fluid supply (not shown) down the interior ofproduction tubing 124 inwellbore 118. Corrosion inhibitor compounds 150 may be allowed to flow down the interior ofproduction tubing 124. Corrosion inhibitor compounds 150 may exitproduction tubing 124 and mix with producedfluids 138. Fluid 130 comprising a corrosion inhibitor may coat any metal surface in which corrosion inhibitor compounds 150 may contact while being placed downhole. Additionally, corrosion inhibitor compounds 150 that may be mixed with produced fluid 138 may be brought back to the surface and may coat any metal surface in which themixture fluid 142 may come in contact with. - The disclosed corrosion inhibitor compounds may also directly or indirectly affect the various downhole equipment and tools that may come into contact with the corrosion inhibitor compounds during operation. Such equipment and tools may include, but are not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, surface-mounted motors and/or pumps, centralizers, turbolizers, scratchers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanical devices, etc.), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc.), control lines (e.g., electrical, fiber optic, hydraulic, etc.), surveillance lines, drill bits and reamers, sensors or distributed sensors, downhole heat exchangers, valves and corresponding actuation devices, tool seals, packers, cement plugs, bridge plugs, and other wellbore isolation devices, or components, and the like. Any of these components may be included in the systems generally described above and depicted in
FIG. 1 . -
FIG. 2 demonstrates a comparison of inhibited corrosion rates from autoclave tests at 250° F. (121° C.). The synthesized carboxamides tests all contained 10 ppm of actives based on the brine volume. The results shown inFIG. 2 illustrate the effectiveness of the synthesized carboxamide corrosion inhibitor compounds as evaluated in a series of autoclave tests. Each test contained 1.17 liters of synthetic field brine, 430 ml of kerosene and a single UNS10180 coupon (27.88 cm2). The test solutions were deaerated and saturated with CO2 at a partial pressure of 19.6 psia (135 KPa), stirred with an inline mixer (1,500 rpm) and heated to 250° F. (121° C.). The corrosion inhibitor compounds were formulated by adding 1 gram of actives to 10 grams of solvent (9% active). The corrosion inhibitor compounds were then injected into the test solutions at 112 ppm, which equates to 10 ppm of actives. The time for completion of the tests ranged from 20 hours to 23 hours. Upon completion of the tests, the coupons were removed from the autoclaves and cleaned in an inhibited acid bath according to ASTM G1 C.3.5. As shown inFIG. 2 , the synthesized products outperformed two commonly used corrosion inhibitor intermediates and several formulated products that are currently used in the oilfield. Intermediates A and A+C resulted in a corrosion rates of 87.7 mpy and 120 mpy, respectively. Formulations Z, Y, and X resulted in corrosion rates of 44 mpy, 151.7 mpy, and 139.9 mpy, respectively. The TEPA/Thiourea/Myristic Acid composition resulted in a corrosion rate of 20.2 mpy. The DETA/Thiorea/Myristic Acid composition resulted in a corrosion rate of 22.5 mpy. The DETA/Thiourea/Lauric Acid composition resulted in a corrosion rate of 27.6 mpy. The compositions of intermediates A, C, X, Y, and Z inFIG. 2 are shown in Table 1. -
TABLE 1 Corrosion Treatment Formulation Inhibitor Active Rate Solvent (%) (%) (ppm) Intermediate methanol (50)/ imidazoline (8) 150 A ethylene glycol (42) Intermediate methanol (48)/ imidazoline (8)/ 145 C ethylene glycol phosphate ester (39.5) (4.5) Formulation water (71)/ethylene complex mixture 200 X glycol (15) (4%) Formulation water (53)/ complex mixture 200 Y methanol (25)/ (7.7%) ethylene glycol (7) Formulation water (56)/ imidazoline (8)/ 200 Z methanol (15) quaternary amine (1)/mercaptan (2) -
FIG. 3 depicts Kettle test results for unsalted synthesized carboxamides using Structures (2) and (3) as shown above in accordance with ASTM G31—Standard Practice for Laboratory Immersion Corrosion Testing of Metals and ASTM G170—Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory. The Kettle tests were continuously purged with anaerobic grade CO2, having a partial pressure of 10.8 psia (74 KPa), 800 ml of sea-salt brine, 80 ml of kerosene, heated to 150° F. (66° C.) and stirred with a magnetic stir bar/plate. The synthesized carboxamides were dissolved in methanol (5% actives) and injected at 100 ppm (5 ppm actives) and then up to 200 ppm (10 ppm actives), based on the total test volume. - A Kettle test using a first composition comprising Structure (2) included a mixture of 38.05 g (0.5 mole) of thiourea and 51.6 g (0.5 mole) of diethylenetriamine (DETA). The mixture was charged to a 250-mL glass kettle equipped with a condenser, a stirrer, and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and lauric acid (100.16 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- A Kettle test using a second composition comprising Structure (2) included a mixture of 38.05 g (0.5 mole) of thiourea and 51.6 g (0.5 mole) of diethylenetriamine (DETA) was charged to a 250-mL glass kettle equipped with a condenser, a stirrer and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and myristic acid (114.2 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- A Kettle test using a composition comprising Structure (3) included a mixture of 76.1 g (1.0 mole) of thiourea and 94.7 g (0.5 mole) of tetraethylenepentamine (TEPA) was charged to a 250-mL glass kettle equipped with a condenser, a stirrer and a gas inlet tube. A slow nitrogen sparge was started. Using an electric heating mantle, the mixture was slowly heated to 170° C. while stirring. The reaction temperature was kept at 170° C. for 4 hours. The mixture was cooled down to 100° C. and myristic acid (114.2 g, 0.5 mole) was added. The mixture was heated back to 170° C. and kept at this temperature for 4 hours with nitrogen purging.
- The baseline or uninhibited corrosion rate was monitored for 0.85 hours before the corrosion inhibitors were injected at 100 ppm (5 ppm actives). At a treatment rate of 100 ppm (5 ppm actives), the average baseline corrosion rate was reduced from 174 mils per year (“MPY”) to 35, 77 and 4 MPY for the DETA/Thiourea/Lauric, DETA/Thiourea/Myristic and TEPA/Thiourea/Myristic reaction product, as depicted in
FIG. 3 . This resulted in inhibition efficiencies of 80, 56 and 97%, respectively. The treatment rate was increased to 200 ppm (10 ppm actives total) at the 4 hour mark for the DETA/Thiourea/Lauric and DETA/Thiourea/Myristic tests, which reduced the corrosion rates to 7 MPY (96% inhibition efficiency) and 62 MPY (64% inhibition efficiency), respectively. -
FIG. 4 depicts Kettle test results for synthesized carboxamides salted with acetic acid in accordance with ASTM G31—Standard Practice for Laboratory Immersion Corrosion Testing of Metals and ASTM G170—Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory. As depicted inFIG. 4 , the synthesized carboxamides were evaluated with Kettle tests run with 810 ml of sea-salt brine, 90 ml of kerosene, and continuously purged with anaerobic grade CO2, with a partial pressure of 10.8 psia (74 KPa). The Kettle tests were heated to 150° F. (66° C.) and stirred with a magnetic stir bar/plate. 1.5 grams of synthesized carboxamides were dissolved in 28.5 grams of methanol and 1.5 grams of acetic acid (5% actives), then injected at 100 ppm (5 ppm actives) up to 200 ppm (10 ppm actives), based on the total test volume. Instantaneous corrosion rate measurements were made with an electrochemical measurement system, using a potentiostat and a linear polarization resistance technique in accordance with ASTM G3—Standard Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing. The potentiostat used a working electrode and a reference electrode and controlled the voltage difference between the working electrode and the reference electrode. Both electrodes were contained in an electrochemical cell, where the potentiostat was used to measure the current flow between the working and reference electrodes. The free-corroding potential, or the potential of the metal in the absence of any net current flow, was scanned over range of +/−13 mV at a rate of 0.4 mV/second. It should be noted that free corrosion potential is the absence of a net electrical current that flows to and from a metal's surface. The free corrosion potential is measured through the voltage difference between the immersed metal and the appropriate reference electrode in a given environment. - It should be noted that the efficiency of a corrosion inhibitor may be calculated by the following formula: Inhibitor Efficiency(%)=100×(CRuninhibited−CRinhibited)/CRuninhibited, where CRuninhibited=the corrosion rate of the uninhibited system, and CRinhibited=the corrosion rate of the inhibited system. In general, the efficiency of a corrosion inhibitor increases with an increase in inhibitor concentration.
- These tests were repeated with the addition of acetic acid (3.2% w/w) to the diluted products. As shown in
FIG. 4 , the Kettle tests were repeated with the addition of acetic acid (3.2% w/w) to the diluted products. The performance of the DETA/Thiourea/Lauric and DETA/Thiourea/Myristic inhibitors improved when salted with acetic acid. At a treatment rate of 100 ppm (5 ppm actives), the average baseline corrosion rate was reduced from 182 MPY to 14, 42 and 17 MPY for the DETA/Thiourea/Lauric, DETA/Thiourea/Myristic and TEPA/Thiourea/Myristic reaction product. This equates to inhibition efficiencies of 92, 77 and 91%, respectively. The treatment rate was increased to 200 ppm (10 ppm actives total) at the 3.5-hour mark for the DETA/Thiourea/Lauric and DETA/Thiourea/Myristic tests, which reduced the corrosion rates to 2 MPY (99% inhibition) and 26 MPY (86% inhibition), respectively. The final inhibition efficiency for the TEPA/Thiourea/Myristic reaction product remained unchanged at 97%. - The foregoing has broadly outlined the features and technical advantages of the embodiments disclosed herein so that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention may be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the invention as set forth in the appended claims.
- Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (20)
1. A method of inhibiting corrosion of a metal surface, comprising:
contacting the metal surface with a corrosion inhibitor compound comprising a substituted carboxamide.
2. The method of claim 1 , further comprising coating the metal surface with the corrosion inhibitor compound.
3. The method of claim 1 further comprising introducing the corrosion inhibitor compound into a wellbore, wherein the metal surface is disposed in the wellbore.
4. The method of claim 1 , wherein the substituted carboxamide comprises the molecular formula:
R1C(O)NR2R3
R1C(O)NR2R3
wherein R1 is selected from the group consisting of a hydrogen, an alkyl group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group;
wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof; and
wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
5. The method of claim 1 , wherein the substituted carboxamide comprises the molecular formula:
6. The method of claim 1 , wherein the substituted carboxamide comprises the molecular formula:
7. The method of claim 1 , wherein the substituted carboxamide comprises the molecular formula:
8. The method of claim 1 , wherein the substituted carboxamide is present in the fluid in an amount of from about 10 ppm to about 500 ppm.
9. The method of claim 1 , wherein the corrosion inhibitor compound is provided in a solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, methanol, glycol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, toluene, xylene, monobutyl ether, hexane, cyclohexane, 2-Butoxyethanol, any organic solvent, aromatic solvents and any combination thereof.
10. The method of claim 3 , wherein the introducing the corrosion inhibitor compound into the wellbore comprises pumping the corrosion inhibitor compound from a fluid supply, through a production tubing, and into the wellbore, and mixing the corrosion inhibitor compound with a produced fluid.
11. The method of claim 10 , further comprising transporting the corrosion inhibitor compound mixed with the produced fluid to a surface of the wellbore, and coating at least one metal surface in which the corrosion inhibitor compound mixed with the produced fluid contacts.
12. The method of claim 4 , wherein R2 is a heteroatom substituted five-membered heterocyclic ring with at least one pendent group comprising a ketone group or a thione group.
13. The method of claim 12 , wherein the heteroatom substituted five-membered heterocyclic ring comprises nitrogen.
14. The method of claim 5 , wherein the substituted carboxamide is alkylated.
15. The method of claim 6 , wherein the substituted carboxamide is alkylated.
16. The method of claim 9 wherein the solvent is present in an amount of about 50 wt % to about 99.5 wt % based on the total weight of the solvent and the corrosion inhibitor.
17. A corrosion inhibitor comprising:
a solvent package; and
a corrosion inhibitor compound comprising a substituted carboxamide having the formula:
R1C(O)NR2R3
R1C(O)NR2R3
wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group,
wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, and
wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
18. The method of claim 17 wherein the solvent package comprises solvent selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethyl formamide, N-methyl pyrrolidone, propylene glycol methyl ether, butyl cellulose, aromatic solvents, and combinations thereof.
19. A system for introducing a corrosion inhibitor into a wellbore, comprising:
a fluid supply containing the corrosion inhibitor, wherein the corrosion inhibitor comprises a corrosion inhibitor compound and a solvent package, wherein the corrosion inhibitor compound comprises a substituted carboxamide; and
a tubular in a wellbore in a subterranean formation, wherein the tubular is in fluid communication with the corrosion inhibitor supply.
20. A system according to claim 19 , wherein the substituted carboxamide has the formula:
R1C(O)NR2R3
R1C(O)NR2R3
wherein R1 is selected from the group consisting of a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, or a heteroatom atom substituted alkenyl group,
wherein R2 is a hydrogen, an alky group, an alkenyl group, a heteroatom substituted alkyl group, a heteroatom atom substituted alkenyl group, or an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof, and
wherein R3 is an alkyl or alkenyl group terminated by a five-membered heterocyclic ring with at least one pendent group comprising a ketone group, a thione group, or any combination thereof.
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