NZ733544A - Method of simply detecting corrosion inhibitor, and composition and kit for simply detecting corrosion inhibitor - Google Patents
Method of simply detecting corrosion inhibitor, and composition and kit for simply detecting corrosion inhibitorInfo
- Publication number
- NZ733544A NZ733544A NZ733544A NZ73354415A NZ733544A NZ 733544 A NZ733544 A NZ 733544A NZ 733544 A NZ733544 A NZ 733544A NZ 73354415 A NZ73354415 A NZ 73354415A NZ 733544 A NZ733544 A NZ 733544A
- Authority
- NZ
- New Zealand
- Prior art keywords
- sulfur
- corrosion inhibitor
- oxidizing
- nickel
- tungsten
- Prior art date
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 126
- 238000005260 corrosion Methods 0.000 title claims abstract description 126
- 239000003112 inhibitor Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims description 34
- 241000894006 Bacteria Species 0.000 claims abstract description 115
- 239000007788 liquid Substances 0.000 claims abstract description 70
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000011593 sulfur Substances 0.000 claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007793 ph indicator Substances 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 17
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 239000001963 growth medium Substances 0.000 claims description 43
- 238000012360 testing method Methods 0.000 claims description 23
- 150000002739 metals Chemical group 0.000 claims description 16
- 239000002738 chelating agent Substances 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical group C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 150000004715 keto acids Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 241000894007 species Species 0.000 claims description 7
- SCWPZQFGCNKGHE-UHFFFAOYSA-J [W+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O Chemical compound [W+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O SCWPZQFGCNKGHE-UHFFFAOYSA-J 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 6
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 6
- 230000035755 proliferation Effects 0.000 claims description 6
- 150000003657 tungsten Chemical class 0.000 claims description 6
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- SOVWEMYVHOLFAD-UHFFFAOYSA-J C(C(=O)[O-])(=O)[O-].[W+4].C(C(=O)[O-])(=O)[O-] Chemical class C(C(=O)[O-])(=O)[O-].[W+4].C(C(=O)[O-])(=O)[O-] SOVWEMYVHOLFAD-UHFFFAOYSA-J 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- 238000011179 visual inspection Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 59
- 238000001514 detection method Methods 0.000 abstract description 11
- 244000005700 microbiome Species 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000002609 medium Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- AYEYSXMZCARQKR-ARGVGCKZSA-N N-methyl-N-(113C)methyl-2-[3-[(1R)-1-pyrazin-2-ylethyl]-1H-inden-2-yl]ethanamine Chemical compound C[C@H](C1=C(CCN(C)[13CH3])Cc2ccccc12)c1cnccn1 AYEYSXMZCARQKR-ARGVGCKZSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000012258 culturing Methods 0.000 description 8
- 229910017053 inorganic salt Inorganic materials 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 241000605179 Thiomonas intermedia Species 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 230000002062 proliferating effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000009630 liquid culture Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- HPQYKCJIWQFJMS-UHFFFAOYSA-N tetrathionic acid Chemical compound OS(=O)(=O)SSS(O)(=O)=O HPQYKCJIWQFJMS-UHFFFAOYSA-N 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- 241000266272 Acidithiobacillus Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GBSWEJRAVNWKCB-UHFFFAOYSA-N C12=C(N=C(N=C2)N2CCNCC2)C(NC2=CC(=C(C=C2)OC2=CC=C3C(=C2)N=CN3C)C)=NC=N1 Chemical compound C12=C(N=C(N=C2)N2CCNCC2)C(NC2=CC(=C(C=C2)OC2=CC=C3C(=C2)N=CN3C)C)=NC=N1 GBSWEJRAVNWKCB-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229940041514 candida albicans extract Drugs 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
- 229940001468 citrate Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- -1 dibasic sodium phosphate anhydride Chemical class 0.000 description 1
- 239000002526 disodium citrate Substances 0.000 description 1
- 235000019262 disodium citrate Nutrition 0.000 description 1
- 235000019524 disodium tartrate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XJRPTMORGOIMMI-UHFFFAOYSA-N ethyl 2-amino-4-(trifluoromethyl)-1,3-thiazole-5-carboxylate Chemical compound CCOC(=O)C=1SC(N)=NC=1C(F)(F)F XJRPTMORGOIMMI-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 239000002824 redox indicator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000002153 sulfur containing inorganic group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/02—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving viable microorganisms
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Zoology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Wood Science & Technology (AREA)
- Plasma & Fusion (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Biotechnology (AREA)
- Biophysics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Provided is a method that enables simple and quick detection of the addition of a corrosion inhibitor for preventing sulfuric acid degradation, due to microorganisms, of sewer system concrete structures, hume pipes and assembled manholes. The method for simple detection of a corrosion inhibitor is characterized in that a sulfur-oxidizing bacterium having sulfur-oxidizing capability, a culture liquid containing sulfur or a sulfur compound that has been adjusted to a pH of 1 to 4, and a sample that is expected to contain a corrosion inhibitor are mixed, and the resulting liquid is set aside for a specific time and then monitored for color change using a pH indicator in order to detect the presence of a corrosion inhibitor. In particular, the corrosion inhibitor detected is nickel or tungsten and the sulfur-oxidizing bacteria is selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans.
Description
METHOD OF SIMPLY DETECTING CORROSION INHIBITOR, AND COMPOSITION AND KIT FOR SIMPLY DETECTING CORROSION Technical Field The present invention relates to a method of simply detecting a corrosion inhibitor included in materials such as concretes containing a corrosion inhibitor such as an antimicrobial agent, and a composition and a kit for simply detecting the corrosion tor used in this method.
Background Art Corrosion of concrete has long been a m in, for example, concrete secondary products such as sewerage concrete structures, Hume pipes, and prefabricated manholes.
Recent findings have indicated that the te corrosion is due to sulfuric acid produced by -oxidizing bacteria proliferating in sewage. To prevent this occurrence of sulfuric acid, technologies have been developed in which metal powder such as nickel and tungsten is ed in concrete as a corrosion inhibitor such as an antimicrobial agent.
Unfortunately, whether or not this kind of the corrosion inhibitor is included in a concrete composition is ly indistinguishable. In addition, there is an idea that for the determination, a colorant such as a dye and a pigment is included in water during concrete kneading to give the concrete a color. In this case, however, because the nt is included while dissolved or dispersed uniformly in the water, it es a large amount of the colorant to be able to ly determine the coloring. Accordingly, the physical properties of the concrete are affected and the colorant spreads over the surface of the concrete product. This has caused such a problem that color transfer, for example, occurs on an object contacting the concrete product.
Patent Literature 1 discloses manufacturing process for a distinguishable additive-containing concrete that can be used to easily and visually determine inclusion of a material (additive) by including a small amount of the material to be determined. Specifically, a fluorescent dye-containing additive (corrosion inhibitor) is kneaded er with a concrete composition, as a powdered additive to be mixed with the concrete composition containing cement and others; to determine inclusion of the fluorescent dye in the concrete, the concrete is ated with invisible light such as black light; and then, scence emitted at the on of the additive is used to visually distinguish the concrete from concrete free of the additive. Of the corrosion inhibitor- containing concrete, the presence of the corrosion inhibitor is detectable in concrete containing the fluorescent dye and the corrosion inhibitor. Unfortunately, the corrosion inhibitor is undetectable in fluorescent dyefree , corrosion inhibitor-containing te.
Patent Literature 2 discloses a method of simply detecting a corrosion tor such that to sulfur bacteria having an iron-oxidizing ability is added an acidic liquid containing nutrient salts for the sulfur bacteria and protein components that promote iron-oxidizing activity; a sample such as concrete ly containing a corrosion tor is added thereto and the mixture is cultured; and a redox indicator is then added and a change in color is detected, so that the ce or absence of the ion tor is detected. This method is a simple innovative method because whether or not a sample such as concrete contains a corrosion inhibitor can be examined in about one day.
Prior Art Literature Patent Literature [Patent Literature 1] Japanese Patent Laid-Open No. 11-1354 [Patent Literature 2] Japanese Patent Laid-Open No. 2014- 189881 Summary of Invention Problems to be solved by the Invention r, a corrosion inhibitor ion method has been sought which can be used to examine, in a shorter time at a site, whether or not a sample such as concrete contains a corrosion inhibitor. In order to find the method, the present inventors have conducted intensive research.
Accordingly, one of the purposes of the present invention is to provide a solution to the above problem and to provide a method of simply detecting a corrosion inhibitor.
Specifically, one of the es is to provide a method which makes it possible to simply and rapidly detect inclusion of a corrosion inhibitor for ting deterioration due to microorganism-derived sulfuric acid in concrete ary products such as sewerage concrete structures, Hume pipes, or prefabricated manholes.
A particular one of the es is to provide a method which makes it possible to detect inclusion of a corrosion inhibitor in a short time at sites such as construction sites.
Another purpose of the present invention is to provide a composition for simply detecting a ion inhibitor, which composition can be advantageously used in the method of simply detecting a corrosion inhibitor according to the present invention.
An additional purpose of the present invention is to provide a kit for simply detecting a corrosion inhibitor, which kit can be advantageously used in the method of simply detecting a corrosion inhibitor according to the present invention.
Means for g the Problems The above purposes can be achieved using a method of simply detecting a corrosion inhibitor, the method comprising: mixing sulfur-oxidizing bacteria having a sulfur-oxidizing ability, a culture medium containing a sulfur compound or sulfur ed to pH 1 to 4, and a sample possibly ning a corrosion inhibitor; allowing the resulting liquid to stand for a n period; and detecting a change in color by means of a pH indicator, so that the presence or absence of the corrosion inhibitor is detected.
[FOLLOWED BY PAGE 5a] - 5a - [0013A] In a particular aspect, the present invention provides a method of simply detecting a ion inhibitor, comprising: mixing -oxidizing bacteria having a sulfuroxidizing ability, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a sample possibly containing a corrosion inhibitor; ng the resulting liquid to stand for a certain period; and detecting a change in color by means of a pH indicator, so that the presence or absence of the ion inhibitor is detected; wherein the corrosion inhibitor is ed from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel and tungsten salts of oxo acid, or nickel or tungsten oxalates; nickel formate and/or tungsten formate as formates; and wherein the sulfur-oxidizing bacteria are at least one s selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans The sulfur-oxidizing bacteria are used under conditions in a culture medium.
[FOLLOWED BY PAGE 6] Preferable embodiments of the method of simply detecting a corrosion inhibitor according to the present invention are as follows. (1) The pH is adjusted from 1 to 3, in particular, from 2 to 3. (2) The pH indicator is thymol blue, methyl orange, bromocresol green, or bromophenol blue. (3) The pH tor is liquid and is added before or after (in particular, before) the certain period of standing. (4) The pH indicator is a test strip which is soaked in the liquid obtained after the certain period of standing. (5) The certain period is from 10 to 60 min. (6) The sulfur-oxidizing bacteria are at least one species selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans. (7) The sulfur-oxidizing ia are a combination of at least one species selected from Acidithiobacillus thiooxidans and hiobacillus ferrooxidans and a sulfur-oxidizing bacterium capable of proliferation in a l pH range. This makes it possible to rapidly detect whether or not a sample contains a corrosion inhibitor not only in an acidic range, but also in a wide range of pH by using the combination of a sulfur-oxidizing ium proliferating in an acidic range and a -oxidizing bacterium proliferating in a neutral range. (8) The -oxidizing bacteria having a sulfuroxidizing ability are those which were pre-cultured and then freed of solid sulfur. That is, the sulfur-oxidizing bacteria are preferably used under conditions in a culture medium. (9) An acid used to adjust the pH is sulfuric acid. (10) The change in color is detected using at least one means of visual inspection and an absorption spectrophotometer. (11) In addition to the sulfur-oxidizing bacteria, the culture medium, and the sample, a or is mixed which forms a chelate compound with a metal that prevents the sulfur-oxidizing bacteria from g but does not form any chelate compound with a metal that is an active ingredient of the corrosion inhibitor. This causes the chelator to form the chelate nd with the metal that is eluted from the sample and ts the sulfur-oxidizing bacteria from growing, thereby inhibiting a decrease in the activity of the sulfur-oxidizing bacteria. In addition, the chelator fails to form a chelate compound with the metal that is an active ingredient of the corrosion inhibitor, so that when the sample contains the corrosion tor, the activity of the sulfur-oxidizing bacteria is inhibited.
Hence, even if the sample contains a metal that prevents the sulfur-oxidizing bacteria from growing, the activity of the sulfur-oxidizing bacteria is maintained, so that r or not the sample contains the corrosion inhibitor is able.
The above es can be achieved using: a composition for simply ing a corrosion inhibitor, sing sulfur-oxidizing bacteria having a sulfuroxidizing ability, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a pH indicator; and a kit for simply detecting a corrosion inhibitor, comprising a first liquid comprising sulfur-oxidizing bacteria having a sulfur-oxidizing ability and a culture medium containing a sulfur nd or sulfur adjusted to pH 1 to 4, and a second liquid comprising a pH indicator. [0017A] In a particular aspect, the present ion provides: a composition when used to detect a corrosion inhibitor, comprising sulfur-oxidizing bacteria having a sulfur-oxidizing ability, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a pH indicator, wherein the corrosion inhibitor is selected from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel or tungsten salts of oxo acid, or nickel or tungsten oxalates; nickel formate and/or tungsten formate as formates; and wherein the -oxidizing bacteria are at [FOLLOWED BY PAGE 8a] - 8a - least one s ed from Acidithiobacillus thiooxidans and Acidithiobacillus xidans; and a kit when used to detect a corrosion inhibitor, comprising a first liquid comprising sulfur-oxidizing bacteria having a sulfur-oxidizing ability and a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a second liquid comprising a pH indicator, wherein the corrosion inhibitor is selected from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel or tungsten salts of oxo acid, or nickel or tungsten oxalates; nickel formate and/or tungsten formate as es; and wherein the sulfur-oxidizing bacteria are at least one species selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans.
The preferable embodiments of the method of simply detecting a corrosion inhibitor according to the present invention are applicable to the composition and kit for simply detecting a ion inhibitor according to the present invention. s of Invention In the method of simply detecting a corrosion inhibitor according to the present invention, sulfuroxidizing bacteria having a sulfur-oxidizing ability, a (followed by page 9) e medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a sample possibly containing a corrosion inhibitor are mixed; the ing liquid is allowed to stand for a certain period; and a change in color is detected by means of a pH indicator, so that the corrosion inhibitor is detected. Because of this, simple work enables the presence or absence of a corrosion inhibitor to be determined in a short period from several dozen minutes to several hours. Hence, the detection test can be carried out even at sites such as construction sites where actual work is in progress as well as the test can be performed rapidly.
Brief Description of gs [Fig. 1] Fig. 1 is a graph indicating a change in the pH at day 0 to day 7 of sulfur oxidizing bacteria-containing liquid of each of Examples A to D in Example 1 of the present invention.
[Fig. 2] Fig. 2 is a graph indicating the number of sulfuroxidizing bacteria at day 5 of sulfur oxidizing bacteriacontaining liquid of each of Examples A to D.
[Fig. 3] Fig. 3 is a graph indicating a change in the pH at 0 to 120 min of sulfur oxidizing ia-containing liquid of each of Examples E to H in e 2 of the present invention.
[Fig. 4] Fig. 4 is a graph ting a change in the pH at 0 to 150 min of sulfur oxidizing ia-containing liquid of each of Examples I to K in Example 3 of the present invention.
[Fig. 5] Fig. 5 is a graph indicating a change in the pH at 0 to 120 min of sulfur ing bacteria-containing liquid of each of Examples L to M in Example 4 of the present Mode for carrying out the Invention A method of simply detecting a corrosion inhibitor according to the present invention is carried out, for example, in accordance with the following steps. i) To a suitable container such as a beaker is added a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4 (preferably, pH = 1 to 3 and more preferably, pH = 2 to 3). ii) A culture medium containing sulfur-oxidizing bacteria having a sulfur-oxidizing ability is put in the container containing the above culture . iii) To the container containing the above sulfuroxidizing bacteria culture medium is added a sample possibly containing a corrosion inhibitor, and the mixture is mixed. The order of addition of these materials is preferably the above-described order, but may be changed.
For example, the sample may first be put in and the sulfuroxidizing bacteria and the culture medium may then be added Examples of the sample possibly ning a corrosion inhibitor include: powder obtained by grinding concrete materials; powder obtained by grinding concrete of construction als; and powder obtained by ng natural rocks. Thus, the sample is, in general, in a powder form. In addition, the culture medium containing a sulfur compound or sulfur is, for example, a sulfuroxidizing ia medium (e.g., 1 L of water contains 3.0 g of ammonium sulfate, 0.5 g of magnesium sulfate, 0.5 g of dibasic potassium phosphate, 0.1 g of potassium chloride, 0.01 g of calcium nitrate, and 10 g of elementary sulfur powder). Preferably, the pH of the culture medium is adjusted to pH 1 to 4 (preferably, pH = 1 to 3 and more preferably, pH = 2 to 3) by adding a suitable amount of sulfuric acid. iv) The resulting mixture liquid is allowed to stand for a certain period, and thereafter, a change in color is ed by means of a pH indicator, so that the presence or absence of the corrosion inhibitor is detected. The pH indicator may be put in when the change in color is ed or may be put in before the certain period of standing. If the pH indicator is put in before the certain period of standing, it is convenient e the change in color can be seen. The certain period should be, in general, at least 10 min. The period is preferably from 10 to 120 min, more preferably from 10 to 60 min, and still more preferably from 10 to 30 min. In the liquid containing the sulfur-oxidizing bacteria having a sulfuroxidizing ability, sulfuric acid is generated by culturing the sulfur-oxidizing ia while using sulfur, etc., so that a low pH (in general, pH 3 or lower) is maintained or is further lowered gradually. By contrast, in the liquid containing the ion inhibitor in the sample, the corrosion inhibitor ts the function of an enzyme which helps generate sulfuric acid in the sulfur-oxidizing bacteria, so that the pH seems to increase (the number becomes larger). Meanwhile, this change in pH appears in a very short time. That is, the method according to the t invention can exploit a phenomenon where a change in pH appears in a very short time when sulfur is used to culture sulfur-oxidizing bacteria in a sample containing a corrosion tor. Thus, the method can be said to be a simple method that makes it possible to detect, in a short time, whether or not a sample contains a corrosion inhibitor.
The temperature at which the liquid is allowed to stand is usually from 20 to 30°C and preferably from 25 to °C. Such conditions are preferable because the activities of microorganisms are most active.
Note that a liquid in which sulfur-oxidizing bacteria, a culture medium, and a sample are mixed and a sample-free liquid may be prepared and both the liquids may be subjected to the step ii) manipulation. This enables ation while a change in color is compared therebetween.
To detect the change in color, visual tion is most simple. The detection can be conducted ically using an absorption spectrophotometer or the tration or amount of the corrosion inhibitor can be detected by using an absorption ophotometer.
The sulfur-oxidizing bacteria having a sulfuroxidizing ability as used in step i) are prepared lly by pre-culturing, followed by removal of solid sulfur.
Attention has been paid to the sulfuric acid production ability of sulfur-oxidizing bacteria, among concrete-corroding microorganisms, that reside in an acidic range and produce sulfuric acid, and the present inventors have found out a method that utilizes this ability and is used to simply detect a corrosion inhibitor. As used herein, any bacteria can be used as long as the bacteria are sulfur-oxidizing bacteria having such a sulfuric acid production ability. Examples of the sulfur-oxidizing bacteria can include Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans.
In addition, the sulfur-oxidizing bacteria that reside in an acidic range may be used in combination with sulfuroxidizing bacteria that can proliferate in a neutral range.
Examples of the sulfur-oxidizing bacteria that can erate in a l range include nas intermedia that proliferates using thiosulfate as an energy .
This makes it possible to rapidly detect whether or not a sample contains a corrosion inhibitor not only in an acidic range, but also in a wide range of pH by using the combination of a sulfur-oxidizing bacterium proliferating in an acidic range and a sulfur-oxidizing bacterium erating in a neutral range.
A method for culturing sulfur-oxidizing bacteria has no particular limitation and may be carried out using normal liquid culture.
For example, Acidithiobacillus thiooxidans may be ated in a 9K liquid culture medium of Silverman et al.
(M.P. Silverman and D.G. Lundgren (1959) J. Bacteriol. 77, 642-647), and the sulfur-oxidizing bacteria may be subjected to shaking culture at 20 to 30°C. Regarding the medium after the liquid culture, it is able that solid sulfur is removed using filter paper from the e medium and the post-filtration culture medium containing the bacteria is then used.
Thiomonas intermedia may be inoculated in a liquid medium (hereinafter, referred to as a neutral sulfuroxidizing bacteria medium) in which, for example, 5 g of yeast extract, 5 g of sodium thiosulfate pentahydrate, 1.5 g of dipotassium hydrogenphosphate, 4.5 g of dibasic sodium phosphate anhydride, 0.1 g of magnesium sulfate heptahydrate, and 0.3 g of ammonium chloride have been added to 1 L of distilled water and the pH is then adjusted using ic acid to 6.0, and the sulfur-oxidizing bacteria may be subjected to g culture at about 30°C.
Meanwhile, Acidithiobacillus thiooxidans (NBI-3 strain) may be ed, for example, as follows.
Specifically, corroded concrete is inoculated in 20 ml of an elementary sulfur inorganic salt medium (at pH 2.5) and the mixture is kept under aerobic conditions at 30°C. When the pH of the medium decreases to 2.0, the medium is changed. This culturing operation is repeated five times.
Cultured Acidithiobacillus tiooxidans is plated on a tetrathionic acid inorganic salt plate medium and a yellow colony is ed. The isolate is used as an NBI-3 strain.
Then, this NBI-3 strain is inoculated in 20 ml of an elementary sulfur inorganic salt medium (at pH 2.5) containing solid sulfur, (NH4)2・SO 4, MgSO4・7H 2O, K2HPO 4, KCl, Ca(NO 3)2・4H 2O etc., and is subjected to shaking culture, for example, at 30°C for 7 days. Here, as described above, the solid sulfur is removed from the medium to give a cultured ial liquid containing the NBI-3 strain.
Thiomonas intermedia can be obtained, for example, as follows. Specifically, paddy field soil at Kozu, Okayamashi , Okayama prefecture is inoculated in 20 ml of a neutral sulfur-oxidizing bacteria medium (at pH 6.0) and the mixture is kept under aerobic conditions at 30°C. When the pH of the medium decreases to 4.0, the medium is changed.
This culturing operation is repeated five times. A white colony of cultured nas edia is isolated to give an isolate.
Then, this e is inoculated in 20 ml of the above neutral sulfur-oxidizing bacteria , and the mixture is subjected to shaking culture, for example, at 30°C for 2 days to give a culture medium containing an isolate of Thiomonas intermedia.
Note that Thiomonas intermedia may not only be isolated, but also a bacterial strain, the NRBC number: NRBC 14564, from the National Institute of Technology and Evaluation (nite) may be used. Further, a commercially available stock bacterial strain may also be used.
In the method ing to the t invention, examples of a culture medium added to sulfur-oxidizing bacteria include media used for the above-mentioned sulfuroxidizing bacteria, namely a 9K basal salt medium or culture media used for an elementary sulfur inorganic salt medium, etc. At that time, to enhance the activity of the sulfur-oxidizing bacteria, elemental sulfur or a sulfur compound is added. Sulfur has 30 or more allotropes and any forms of sulfur can be used. Among the allotropes, cyclic S8 sulfur is y used. The S8 sulfur has three crystal forms: a-sulfur (rhombic sulfur), b-sulfur (monoclinic sulfur), and g-sulfur (monoclinic sulfur). The rhombic sulfur is stable and is thus preferable. es of the sulfur compound can include sulfur-containing inorganic compounds, for example, sulfides such as a metal sulfide and tetrathionic acid. Preferred is elemental sulfur (also referred to as elementary sulfur or solid sulfur).
Note that when the sulfur-oxidizing bacteria (Thiomonas intermedia) capable of proliferation in a l range is used in combination, it is preferable to add, as an energy source, a lfate to the medium.
An appropriate amount of a suitable acid is added to the e medium containing sulfur, etc., and the pH of the liquid is ed from 1 to 4 (preferably, pH = 2 to 3 and more preferably, 2.5). es of the acid used can include sulfuric acid. Other acids (e.g., sulfurous acid, hydrochloric acid, nitric acid, nitrous acid, phosphoric acid, thiocyanic acid, carbonic acid, and boric acid) inhibit growth of sulfur bacteria, and cannot thus be of general use.
In step ii), the pH-adjusted liquid is allowed to stand for a certain period, and thereafter, a change in color is detected by means of a pH indicator, so that the presence or absence of the corrosion inhibitor is detected.
The above period of standing is usually 10 min or more, preferably from 10 to 120 min, more preferably from 10 to 60 min, and still more preferably from 15 to 45 min. The shorter the period, the more preferable, because the detection time can be shortened. To e this, it is necessary to adjust the concentration of the oxidizing bacteria and the kind of the culture medium, etc.
The concentration of the sulfur-oxidizing bacteria, in particular, should be appropriate. For example, when the amount of the mixture liquid is 100 ml, the number of the sulfur-oxidizing bacteria having a sulfur-oxidizing ability ranges preferably from 2 to 20 ´ 108 cells/100 ml and more preferably from 4 to 10 ´ 108 cells/100 ml. The calculated content of sulfur in the culture medium containing sulfur or a sulfur nd is from 0.2 to 2.0 g/100 ml and more preferably from 0.5 to 1.5 g/100 ml. It is preferable to use 100 to 200 mg, in particular, 100 mg of the sample per 100 ml of the above mixture liquid. The m amount of the sulfur bacteria proliferating in the culture medium is usually from 5 to 10 ´ 108 cells/ml.
Examples of the corrosion inhibitor can include: metals such as nickel , tungsten, , cobalt, copper, and an alloy thereof; oxides of these metals; metal salts of the containing oxo acid, or metal oxalates; organic compounds such as metal formates; and zeolitesupported materials therefrom (provided that the metal of such metal salts is usually an alkali metal or an alkalineearth metal). According to the present invention, particularly red are Na2WO 4 and nickel powder.
The mixture liquid as obtained by mixing the sulfuroxidizing bacteria and the sample, etc., usually has a pH of 3 or less at the time of mixing. In the case of there being a corrosion tor, however, the sulfur-oxidizing bacteria are prevented from proliferating. This blocks the production of sulfuric acid, leading to a gradual increase in pH. It is preferable to use, as an indicator, a pH indicator through which this increase causes a change in color to appear. Specifically, preferred is a pH indicator which causes a color to change when the pH is 4 or higher, in ular, from 4 to 6. Examples of such a pH indicator can include thymol blue, methyl orange, bromocresol green, bromophenol blue, methyl red, and bromocresol purple. Preferred are thymol blue, methyl orange, resol green, and henol blue.
Further, when the sulfur-oxidizing bacteria and the sample, etc., are mixed, it is possible to admix them with a chelator which forms a chelate compound with a metal that prevents the sulfur-oxidizing bacteria from growing but does not form any chelate compound with a metal that is an active ient of the corrosion inhibitor.
Representative examples of the metal that prevents the sulfur-oxidizing bacteria from growing include, but are not limited to, hexavalent chromium.
The metal which is an active ingredient of the corrosion inhibitor is discussed in the section regarding the corrosion inhibitor.
Any chelator may be good as long as the chelator is a or which forms a chelate compound with a metal that prevents the sulfur-oxidizing bacteria from growing but does not form any chelate compound with a metal that is an active ingredient of the corrosion inhibitor. Specific examples can e disodium ethylenediaminetetraacetate, tartrate, citrate, and oxalate. Preferred is disodium ethylenediaminetetraacetate.
The amount of the or added ranges from 0.05 to 0.30 mass% per mixture liquid such as the culture medium before the sample is added and preferably from 0.10 to 0.25 mass%.
Addition of the chelator causes the chelator to form the chelate compound with the metal that is eluted from the sample and prevents the sulfur-oxidizing bacteria from growing, y inhibiting a decrease in the activity of the sulfur-oxidizing ia. In addition, the chelator fails to form the chelate compound with the metal that is an active ingredient of the corrosion inhibitor, so that when the sample ns the corrosion inhibitor, the activity of the sulfur-oxidizing bacteria is inhibited.
Hence, even if a sample contains a metal that prevents the sulfur-oxidizing bacteria from g, the activity of the sulfur-oxidizing bacteria is maintained, so that whether or not the sample contains a corrosion inhibitor is detectable.
The present invention also provides a composition for simply detecting a corrosion inhibitor and a kit for simply detecting the corrosion tor, such that they can be advantageously used in the method of simply detecting a corrosion inhibitor according to the present invention.
The composition for simply detecting a corrosion inhibitor according to the present invention comprises a culture medium for the above-described sulfur-oxidizing bacteria having a sulfur-oxidizing ability, a culture medium containing a sulfur nd or sulfur adjusted to pH 1 to 4, and a pH tor. When the resulting mixture is used to implement the detection , a sample should be added to the mixture.
In addition, the mixture may contain the above chelator.
The kit for simply detecting a corrosion inhibitor according to the present invention comprises a first liquid comprising a e medium for sulfur-oxidizing bacteria having a sulfur-oxidizing y and a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a second liquid comprising a pH indicator.
Alternatively, three kinds of liquid: a culture medium for sulfur-oxidizing bacteria having a sulfur-oxidizing y, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a liquid containing a pH indicator may each be separated. The above pH indicator may be a pH test strip.
In addition, the above chelator may be included in any of the above liquids.
Regarding the above composition and kit for simply detecting a corrosion inhibitor, the number of sulfuroxidizing bacteria having a sulfur-oxidizing ability ranges ably from 2 to 20 ´ 108 cells/100 ml and more preferably from 4 to 10 ´ 108 cells/100 ml. The calculated content of sulfur in the culture medium containing sulfur or a sulfur compound is from 0.2 to 2.0 g/100 ml and more ably from 0.5 to 1.5 g/100 ml. The above ranges are values when the total amount of the composition or kit is set to 100 ml, and are typically used per 100 to 200 mg of a sample. Accordingly, when the total amount of the ition or kit is made larger or smaller, this concentration is preferably kept for the design.
Examples [Example 1] (1) Preparation of Sulfur-oxidizing ia Culture Medium.
First, 1.0 g of ed concrete was inoculated in 20 ml of an elementary sulfur inorganic salt medium (at pH 2.5) containing 1.0% of elementary sulfur, 0.3% of (NH 4)2SO 4, 0.05% of MgSO4-7H 2O, 0.05% of K2HPO 4, 0.01% of KCl, and 0.001% of Ca(NO3)2×4H 2O, and the mixture was kept under aerobic conditions at 30°C. When the pH of the medium decreased to 2.0 or lower, the medium was d. This culturing operation was repeated five times. ed Acidithiobacillus thiooxidans was plated on a tetrathionic acid inorganic salt plate medium and a yellow colony was isolated. This isolate was used as an NBI-3 strain.
The above NBI-3 strain was added to 20 ml of an elementary sulfur inorganic salt medium (an elemental sulfur 9K basal ; pH 2.5) containing 1% of elemental sulfur, 0.3% of (NH4)2SO 4, 0.05% of MgSO4-7H 2O, 0.05% of K2HPO 4, 0.01% of KCl, and 0.001% of Ca(NO3)2×4H 2O, and the mixture was subjected to shaking culture for 1 week. The number of the bacteria in the resulting NBI-3 strain culture medium was 7 ´ 108 cells/ml. (2) Detection of Corrosion tor Example A) To a 500-mL Erlenmeyer flask were added 1.0 mL (the cell number: 5 to 10 ´ 108 cells/ml) of the sulfuroxidizing ia (NBI-3 strain) as obtained in the above section (1), 250 mL of a 9K basal salt medium adjusted using sulfuric acid to pH 2.5, and 2.5 g of elemental sulfur. Further, 500 mg of Bicrete (antibacterial concrete (concrete containing, as corrosion inhibitors, sodium tungstate and metal nickel); manufactured by HIDA CO.) was added.
The resulting liquid was tested using a thymol blue test strip (which was red when the reaction started) as a pH indicator to visually observe a change in color over time.
The above 9K basal salt medium has the following composition: acidic water at pH 2.5 contains the following inorganic salts (0.3% of ammonium e, 0.05% of magnesium sulfate, 0.05% of c potassium phosphate, 0.01% of potassium chloride, and 0.001% of calcium sulfate).
In addition, with respect to the elementary sulfur inorganic salt medium used for culturing the NBI-3 strain, sulfur-oxidizing bacteria, elementary sulfur was added at 1% to the above 9K basal salt medium while the pH was adjusted using sulfuric acid to pH 2.5.
As the above Bicrete, used was a ed one (with an average particle size of about 100 mm) as obtained by grinding, with a wire brush, the surface of a Bicrete pipe.
Concrete free of a corrosion inhibitor was likewise processed to give a ed one.
Example B) The same procedure as in Example A was repeated except that 1.0 mL of the sulfur-oxidizing bacteria was changed to 2.0 mL. The resulting liquid was tested using a thymol blue test strip (which was red when the reaction started) as a pH indicator to visually observe a change in color over time.
Example C) (Comparison) The same procedure as in Example A was repeated except that concrete free of a corrosion inhibitor was used as an alternative for the Bicrete. The resulting liquid was tested using a thymol blue test strip (which was red when the reaction started) as a pH indicator to visually e a change in color over time. e D) (Comparison) The same procedure as in Example B was repeated except that concrete free of a corrosion inhibitor was used as an alternative for the Bicrete. The resulting liquid was tested using a thymol blue test strip (which was red when the reaction d) as a pH indicator to visually observe a change in color over time.
(Results) After one day, the liquid of each of Example A and Example B was d from red to yellow.
Fig. 1 is a graph indicating a change in pH at day 0 to day 7.
Fig. 2 is a graph indicating the cell number of sulfur-oxidizing bacteria after five days. The cell number of sulfur-oxidizing bacteria was determined with a spectrophotometer by reading absorbance at a wavelength of 660 nm bance (A660nm)). When the bacteria grew in the liquid e , the culture medium d from transparent to turbid. The level of turbidity anied by the growth of the bacteria was proportional to the absorbance at 660 nm m), so that the above reading was used to determine how much the sulfur-oxidizing bacteria had grown.
[Example 2] (1) Preparation of Sulfur-oxidizing Bacteria Culture Medium.
The same procedure as in Example 1 was repeated. (2) Detection of Corrosion Inhibitor Example E) To a 200-mL Erlenmeyer flask were added 0.2 mL of the sulfur-oxidizing bacteria culture medium as obtained in the above section (1), 50 mL of a 9K basal salt medium adjusted using sulfuric acid to pH 2.5, and 0.5 g of elemental sulfur. Further, 100 mg of Bicrete (antibacterial concrete (concrete containing, as corrosion inhibitors, sodium tungstate and metal ); ctured by HIDA CO.) was added.
The resulting liquid was tested using a piece of bromocresol green test paper (which was yellow when the reaction started) as a pH indicator to visually e a change in color over time every 15 min.
Example F) The same procedure as in Example E was repeated except that 0.2 mL of the sulfur-oxidizing bacteria was d to 0.4 mL. While the resulting liquid was tested using, as a pH indicator, a piece of bromocresol green test paper (which was yellow when the reaction started), a change in color over time was visually observed every 15 min. e G) (Comparison) The same procedure as in Example E was repeated except that concrete free of a corrosion inhibitor was used as an alternative for the Bicrete. The resulting liquid was tested using a piece of bromocresol green test paper (which was yellow when the reaction started) as a pH indicator to visually observe a change in color over time every 15 min.
Example H) (Comparison) The same procedure as in Example F was repeated except that concrete free of a corrosion inhibitor was used as an alternative for the Bicrete. The resulting liquid was tested using a piece of resol green test paper (which was yellow when the reaction started) as a pH indicator to visually observe a change in color over time every 15 min.
(Results) After 30 min, the liquid of each of Example E and e F was changed from yellow to green, and after 60 min, the color was changed to blue.
Fig. 3 is a graph indicating a change in pH from 0 to 120 min.
[Example 3] (1) Preparation of Sulfur-oxidizing Bacteria Culture Medium.
The same ure as in Example 1 was repeated. (2) Detection of Corrosion Inhibitor Example I) To a 100-mL Erlenmeyer flask were added 1.2 mL of the sulfur-oxidizing bacteria as obtained in the above section (1), 50 mL of a sulfur bacteria medium adjusted using sulfuric acid to pH 2.5, and 0.5 g of tal sulfur.
Further, 100 mg of a corrosion inhibitor-free concrete sample 1 was added.
The resulting liquid was tested using a piece of bromocresol green test paper (which was yellow when the reaction d) as a pH indicator, to ly inspect a change in color over time every 15 min.
The same procedure as in Example I was repeated except that the concrete sample 1 was changed to an unknown concrete sample 2. The resulting liquid was tested using a piece of bromocresol green test paper (which was yellow when the reaction started) as a pH indicator to visually inspect a change in color over time every 15 min.
Example K) The same procedure as in Example I was repeated except that the concrete sample 1 was changed to an unknown concrete sample 3. The resulting liquid was tested using a piece of bromocresol green test paper (which was yellow when the reaction started) as a pH indicator to visually inspect a change in color over time every 15 min.
(Results) After 15 min, the liquid of e J was changed from yellow to green, the liquid of Example K was changed from yellow to blue, and the color of the liquid of Example I was unchanged. Fig. 4 is a graph indicating a change in pH from 0 to 150 min.
The above results demonstrate that the concrete of each of Example J and Example K contains a corrosion inhibitor and the concrete of Example I fails to contain a corrosion inhibitor. le 4] In this Example, in on to the sulfur-oxidizing bacteria used in Examples 1 to 3 (hereinafter, referred to as the first sulfur-oxidizing bacteria), sulfur-oxidizing bacteria e of proliferation in a neutral range (hereinafter, referred to as the second sulfur-oxidizing bacteria) were used as -oxidizing bacteria. ile, the present inventors tried to reproduce the test using Example G) and Example H) of Example 2. In this case, even if the concrete free of a corrosion inhibitor was added, the s were inconsistent with the results of Example 2 and demonstrated that there were several concrete samples in which the pH was not lowered, but was increased, and the color of the liquid remained blue. When Bicrete, which contains corrosion inhibitors, was added, the color of the liquid should become blue, so that both are indistinguishable.
Then, the following test for detecting a corrosion inhibitor was carried out, which test can be used to determine the presence or absence of the corrosion inhibitor even if such unreproducible concrete is used (1) Preparation of First Sulfur-oxidizing Bacteria Culture Medium.
The same ure as in Example 1 was repeated. (2) Preparation of Second Sulfur-oxidizing ia e Medium.
First, 1.0 g of a soil sample collected from a paddy field at Kozu, Okayama-shi, a prefecture was inoculated in 20 ml of a l sulfur-oxidizing bacteria medium (at pH 6.0) and the mixture was kept under aerobic conditions at 30°C. When the pH of the medium decreased to 4.0 or lower, the medium was changed. This culturing operation was repeated five times. A white colony of cultured Thiomonas intermedia was isolated to give an isolate.
Further, this isolate was added to 20 ml of a fresh neutral sulfur-oxidizing bacteria medium (pH 6.0), and the mixture was subjected to shaking culture at 30°C for 2 days.
The number of the bacteria in the resulting isolate culture medium was 2 ´ 109 cells/ml. (3) Detection of Corrosion Inhibitor Example L) To each of three 50-mL Falcon (a registered trademark) conical tubes (manufactured by Corning Inc.) were added 0.2 mL of the first sulfur-oxidizing bacteria as ed in the above section (1), 0.1 mL of the second sulfuroxidizing bacteria as obtained in the above section (2), 20 mL (pH 2.5) of a 9K basal salt medium adjusted using sulfuric acid to pH 2.5, 250 mg of elemental sulfur, 3.3 mL (pH 2.0) of 0.1 M b-alanine sulfate buffer solution at pH 2.0, 22.3 mg of disodium ethylenediaminetetraacetate, 1.0 mL of a bromocresol green solution, and 100 mg of sodium thiosulfate. At this time point, the pH of the liquid was 2.75.
Further, 100 mg of each of the above unreproducible concrete samples 1 to 3 was added to each of the above 3 Falcon (a registered ark) conical tubes (hereinafter, referred to as respective Example L-1, Example L-2, and e L-3). A change in liquid color over time was visually observed after from 10 min to 120 min, and the pH was measured at the same time. Note that L-1 to 3 are averaged to indicate a measured pH value.
The same procedure as in Example L) was repeated except that Bicrete samples 1 to 3 were used as alternatives for the unreproducible concrete samples 1 to 3.
A change in the liquid color over time of each of the resulting liquids (hereinafter, the resulting liquids are referred to as respective Example M-1, Example M-2, and Example M-3) was visually observed after from 10 min to 120 min, and the pH was measured at the same time. Note that M-1 to 3 are ed to indicate a measured pH value.
(Results) Fig. 5 shows that while the liquid of each of Examples L-1 to L-3 was d from yellow to only green after 120 min, the liquid of each of Examples M-1 to M-3 was changed from yellow to blue. The difference in liquid color between the both was distinguishable after 10 min.
In addition, the same figure shows that a big difference in pH between the Example L samples and the Example M samples occurred at 30 min after initiation of the test and was about 2; and the difference continued to become larger until 120 min.
The above results were results that made it possible to determine that the concrete of each of es L-1 to L-3 did not contain a corrosion tor and the concrete of each of es M-1 to M-3 contained a corrosion inhibitor.
When the present inventors tried to reproduce the test using Example G) and Example H) of Example 2, no reproducible results were obtained. This seems to be because (i) when the concrete is free of a corrosion inhibitor, but contains a large amount of alkali components such as sodium and potassium, the initial pH of the liquid at the time of the corrosion inhibitor detection test is high; and (ii) elution of harmful metals such as hexavalent chromium from the concrete causes the activity of the sulfur-oxidizing bacteria to decrease.
By contrast, the activity of the -oxidizing ia was activated by combining the sulfur-oxidizing bacteria capable of proliferation in an acidic range with the sulfur-oxidizing bacteria capable of proliferation in a l range and by adding a chelator to convert the harmful metals such as hexavalent chromium to an insoluble fixed material. Consequently, it can be inferred that the presence or absence of a corrosion inhibitor can be ined even in the case of using the concrete indistinguishable in the test of Example 2.
Industrial Applicability It can be seen that use of the t method makes it possible to rapidly find out whether or not there is a ion inhibitor in a ng or a material such as concrete. Hence, the use of this method makes it possible to rapidly detect whether or not there is a corrosion inhibitor in concrete of a building already built. In addition, it is possible to immediately find out, at a construction site, the presence or absence of a corrosion inhibitor. Further, the present method can be exploited for quality management to inspect whether or not a corrosion tor is actually included in a material such as concrete for which inclusion of the corrosion tor is designed.
Claims (13)
1. A method of simply detecting a corrosion inhibitor, sing: mixing sulfur-oxidizing ia having a sulfuroxidizing ability, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a sample possibly containing a corrosion inhibitor; allowing the resulting liquid to stand for a certain period; and detecting a change in color by means of a pH indicator, so that the presence or e of the corrosion inhibitor is detected; wherein the corrosion inhibitor is selected from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel or tungsten salts of oxo acid, or nickel or tungsten es; nickel formate and/or tungsten formate as formates; and n the sulfur-oxidizing bacteria are at least one species selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans.
2. The method of simply detecting a corrosion inhibitor according to claim 1, wherein the pH is adjusted from 2 to
3. The method of simply detecting a ion tor according to claim 1 or 2, wherein the pH indicator is thymol blue, methyl orange, bromocresol green, or bromophenol blue.
4. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 3, wherein the pH tor is liquid and is added before or after the certain period of standing.
5. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 3, n the pH indicator is a test strip which is soaked in the liquid obtained after the certain period of standing.
6. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 5, wherein the certain period is from 10 to 60 min.
7. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 6, wherein the sulfur-oxidizing bacteria are a ation of at least one species selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans and a sulfur-oxidizing bacterium capable of proliferation in a neutral pH range.
8. The method of simply ing a corrosion tor according to any one of claims 1 to 6, wherein the sulfuroxidizing ia having a sulfur-oxidizing ability are those which were pre-cultured and then freed of solid sulfur.
9. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 8, wherein an acid used to adjust the pH is sulfuric acid.
10. The method of simply detecting a corrosion inhibitor according to any one of claims 1 to 8, wherein the change in color is detected using at least one means of visual inspection and an absorption spectrophotometer.
11. The method of simply detecting a corrosion inhibitor ing to any one of claims 1 to 10, wherein in addition to the sulfur-oxidizing bacteria, the culture medium, and the sample, a chelator is mixed which forms a e compound with a metal that prevents the sulfur-oxidizing bacteria from growing but does not form any chelate compound with a metal that is an active ingredient of the corrosion inhibitor.
12. A composition when used to detect a corrosion inhibitor, sing sulfur-oxidizing bacteria having a sulfur-oxidizing ability, a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a pH indicator, wherein the corrosion inhibitor is selected from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel or tungsten salts of oxo acid, or nickel or tungsten es; nickel formate and/or tungsten formate as es; and wherein the sulfur-oxidizing bacteria are at least one species selected from Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans.
13. A kit when used to detect a corrosion inhibitor, comprising a first liquid sing -oxidizing ia having a sulfur-oxidizing ability and a culture medium containing a sulfur compound or sulfur adjusted to pH 1 to 4, and a second liquid comprising a pH indicator, wherein the corrosion inhibitor is selected from the group consisting of metals wherein the metal is nickel, tungsten, and an alloy thereof; oxides of these metals; nickel or tungsten salts of oxo acid, or nickel or tungsten oxalates; nickel formate and/or tungsten formate as formates; and wherein the sulfur-oxidizing bacteria are at least one species selected from hiobacillus thiooxidans and Acidithiobacillus ferrooxidans. [
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2014/083892 WO2016103320A1 (en) | 2014-12-22 | 2014-12-22 | Method for simple detection of corrosion inhibitor, as well as composition for simple detection and kit for simple detection of corrosion inhibitor |
| PCT/JP2015/085712 WO2016104447A1 (en) | 2014-12-22 | 2015-12-21 | Method for simple detection of corrosion inhibitor, as well as composition for simple detection and kit for simple detection of corrosion inhibitor |
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| CN107841741B (en) * | 2017-10-13 | 2018-11-27 | 乾乐欣展新材料技术（上海）有限公司 | A kind of aluminum substrate surface biological processing oxidation technology |
| CN118411159B (en) * | 2024-07-02 | 2024-10-18 | 四川宏大安全技术服务有限公司 | Shale gas production pipeline sterilization corrosion inhibitor filling optimization method |
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| JP6073728B2 (en) * | 2013-03-28 | 2017-02-01 | 株式会社安藤・間 | Simple detection method for corrosion inhibitor, simple detection composition for corrosion inhibitor, and simple detection kit |
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