KR20190067015A - Carbohydrazide containing water treatment coloring composition for power plant boiler system - Google Patents
Carbohydrazide containing water treatment coloring composition for power plant boiler system Download PDFInfo
- Publication number
- KR20190067015A KR20190067015A KR1020170166971A KR20170166971A KR20190067015A KR 20190067015 A KR20190067015 A KR 20190067015A KR 1020170166971 A KR1020170166971 A KR 1020170166971A KR 20170166971 A KR20170166971 A KR 20170166971A KR 20190067015 A KR20190067015 A KR 20190067015A
- Authority
- KR
- South Korea
- Prior art keywords
- carbohydrazide
- power plant
- water
- boiler
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000004040 coloring Methods 0.000 title abstract description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 21
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 20
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 14
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 14
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 239000002455 scale inhibitor Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 30
- 239000001301 oxygen Substances 0.000 abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 abstract description 30
- 239000001569 carbon dioxide Substances 0.000 abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 9
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 231100000053 low toxicity Toxicity 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003183 carcinogenic agent Substances 0.000 description 4
- -1 however Chemical compound 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000357 carcinogen Toxicity 0.000 description 3
- 230000003635 deoxygenating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100001231 less toxic Toxicity 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 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
- 238000002845 discoloration Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NOVHEGOWZNFVGT-UHFFFAOYSA-N hydrazine Chemical compound NN.NN NOVHEGOWZNFVGT-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
-
- 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
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
본 발명은 발전소 보일러 계통수 중의 산소 부식과 이산화탄소 부식을 억제할 수 있는 색조용 조성물에 관한 것으로서, 구체적으로는 용존 산소 제거율이 높고 독성이 낮은 카보히드라지드를 포함하는 발전소 보일러 계통의 수처리 조성물 및 이를 이용한 산소 부식과 이산화탄소 부식을 억제하는 방법에 관한 것이다. 또한 용존 산소의 농도에 대해서 육안으로 식별이 가능한 조성물을 제공한다.The present invention relates to a composition for a coloring composition capable of inhibiting oxygen corrosion and carbon dioxide corrosion in power plant boiler system water, and more specifically, to a water treatment composition of a boiler system of a power plant including a carbohydrazide having a high dissolved oxygen removal rate and low toxicity, Oxygen corrosion and carbon dioxide corrosion. It also provides a visually identifiable composition for the concentration of dissolved oxygen.
보일러는 물을 가열해 필요한 증기 또는 온수를 만드는 장치이며, 사용 목적에 따라 여러 형식의 보일러가 있다. 국내 발전설비는 대부분 고온 고압의 대용량 보일러를 사용하고 있으며, 급수 및 보일러수의 수질관리를 위한 수처리를 시행하고 있다. 수처리는 발전설비의 운전 효율을 높이고 수명을 연장하는데 그 목적을 두고 있다.A boiler is a device that heats water to make necessary steam or hot water. There are various types of boilers depending on the purpose of use. Most domestic power generation plants use high-capacity, high-pressure boilers, and water treatment for water quality control of water supply and boiler water is being implemented. The purpose of water treatment is to increase the operation efficiency and extend the life span of power generation facilities.
수처리는 계통수에 적절한 약품을 처리하는 것으로서 계통수 수질을 향상시키고 계통 구성재질의 부식을 막는 효과가 있다. 각 발전소에서는 해당 발전소 보일러의 특성 및 조건에 적합한 수처리 방법을 채택하여 사용하고 있다.Water treatment improves the quality of the system water and prevents the corrosion of system components. Each power plant adopts a water treatment method suitable for the characteristics and conditions of the power plant boiler.
보일러 계통의 부식에 의한 보일러 튜브의 손상은 발전설비의 운전정지를 유발하는 가장 큰 원인으로 운전정지에 따른 비용손실과 보수비용 등 막대한 경제적 손실을 초래한다. 발전소 계통 구성재질 부식발생의 주요 원인으로 계통수 중 부식성 이온의 존재, 용존 가스의 존재 등 여러 요인들이 있을 수 있으나 용존 산소가 계통 재질의 부식에 가장 큰 영향을 끼치고 있는 것으로 알려져 있다.Damage of the boiler tube due to corrosion of the boiler system is the biggest cause of the operation stoppage of the power generation facility, which causes a great economic loss such as the cost loss due to the operation stoppage and the maintenance cost. It is known that dissolved oxygen has the greatest influence on the corrosion of system materials, although there are many factors such as presence of corrosive ions and presence of dissolved gas in the systematic water.
보일러 계통수의 용존 산소를 제거하기 위한 방법으로 기계적 용존 산소 제거방법인 탈기기에 의한 1차적 용존 산소의 제거와 탈기기에서 제거하지 못한 잔여 용존 산소를 제거하기 위한 탈산소제를 사용하는 2차적 화학적 용존 산소 제거방법이 있다.As a method to remove dissolved oxygen in the boiler system, it is necessary to remove the primary dissolved oxygen by deaerator which is a mechanical dissolved oxygen removing method and secondary chemical dissolution using deoxidizer to remove residual dissolved oxygen which is not removed by deaerator There is an oxygen removal method.
현재 대부분 국내 발전용 보일러에서는 탈산소제로 전투기의 연료로도 사용되고 있는 히드라진 (Hydrazine, N2H4)을 사용하고 있으나, 히드라진은 인체 발암성이 높고 호흡기, 피부 등에 영향을 미칠 수 있는 유독성의 물질로 밝혀졌다.Currently, most domestic power generation boilers use hydrazine (N 2 H 4 ), which is also used as fuels for deoxidizing fuels, but hydrazine is toxic substance that has high human carcinogenicity and may affect respiratory, skin, .
히드라진이 유사 발암성물질이라는 사실이 발견된 이후 선진국에서는 히드라진을 사용할 때 극도의 주의를 요구하고 있으며 히드라진의 배출 및 보관에 관해 엄격한 규제를 취하고 있다. 그러나 화학물질안전원에 따르면 2013년 국내 히드라진(히드라진 수화물 형태)의 배출량은 년간 1,992kg으로서 적지 않은 양이며, 히드라진을 포함하는 폐수 및 폐기물은 각각 년간 16,954kg, 56,794kg으로 밝혀져 향후 히드라진 배출에 대한 규제가 엄격해질 것으로 예상된다.Since the discovery that hydrazine is a pseudo-carcinogen, advanced countries require extreme caution when using hydrazine and have strict regulations on hydrazine emissions and storage. However, according to the Chemical Safety Agency, the amount of hydrazine hydrazine (hydrazine hydrate form) in Korea in 2013 is 1,992 kg per year, and the amount of waste water and waste including hydrazine is 16,954 kg and 56,794 kg per year, Regulation is expected to become strict.
미국 등 세계 각국의 보일러 수처리 약품 제조회사들과 발전회사들은 수십 년 전부터 히드라진을 대체할 수 있는 다양한 종류의 대체 탈산소제를 개발하여 발전용 보일러 및 산업용 보일러에 대체 적용해오고 있다.The United States and other countries have developed alternate deoxidizing agents that can replace hydrazine for decades ago and have been applied to power boilers and industrial boilers.
현재 개발되어 상용화되거나 상용화 추진중인 주요 대체 탈산소제로는 카보히드라지드 (Carbohydrazide), 히드로퀴논 (Hydroquinone), 디에틸히드록실아민 (Diethyl hydroxylamine), MEKO (Methyl ethyl ketoxime), 아스코르빈산 (Ascorbic Acid) 등이 있다.Major alternative deoxygenating agents that are currently being developed and commercialized or being promoted for commercial use include Carbohydrazide, Hydroquinone, Diethyl hydroxylamine, Methyloethyl ketoxime (MEKO), Ascorbic Acid, .
상기 대체 탈산소제 중 카보히드라지드는 아래 반응식과 같이 용존 산소와 반응하여 물 및 이산화탄소를 생성한다. 카보히드라지드는 85℃까지는 히드라진보다 용존 산소 제거 속도가 높은 것으로 알려져 있으며, 150℃까지는 가수분해되어 히드라진과 이산화탄소를 생성하며, 200℃ 이상에서는 암모니아, 질소, 수소로 분해된다. 그러나 카보히드라지드는 히드라진과 달리 발암 물질로 인식되지 않고, 히드라진에 비해서 독성도 낮은 것으로 알려져 있다.The carbohydrazide in the alternative deoxygenating agent reacts with dissolved oxygen to produce water and carbon dioxide as shown in the following reaction formula. Carbohydrazide is known to have a higher dissolved oxygen removal rate than hydrazine up to 85 ° C. It hydrolyzes to 150 ° C to generate hydrazine and carbon dioxide, and decomposes to ammonia, nitrogen and hydrogen at temperatures above 200 ° C. Unlike hydrazine, however, carbohydrazide is not recognized as a carcinogen and is less toxic than hydrazine.
(H2N-NH)2CO + 2O2 → 2N2 + 3H2O + CO2 (H 2 N-NH) 2 CO + 2O 2 → 2N 2 + 3H 2 O + CO 2
디에틸히드록실아민 (Diethyl hydroxylamine)은 아래 반응식과 같이 용존 산소와 반응하여 아세트산 및 물을 생성한다. 디에틸히드록실아민 또한 카보히드라지드와 마찬가지로 발암 물질로 인식되지 않고, 히드라진에 비해서 독성이 낮다.Diethyl hydroxylamine reacts with dissolved oxygen to produce acetic acid and water as shown in the following reaction formula. Diethylhydroxylamine, like carbohydrazide, is not recognized as a carcinogen and is less toxic than hydrazine.
4(C2H5)2NOH + 9O2 → 8CH3COOH + 2N2 + 6H2O4 (C 2 H 5 ) 2 NOH + 9O 2 → 8CH 3 COOH + 2N 2 + 6H 2 O
모르폴린(Morpholine)은 휘발성 아민인 C4H9NO 화합물로서 탈산소재를 포함하는 조성물의 대표적인 첨가제다.Morpholine is a typical additive for compositions containing deacidified materials as C 4 H 9 NO compounds which are volatile amines.
공정 열 교환 및 발전용으로 사용되는 산업용 보일러에서 발생하는 스팀은 이용된 후 응축되어 다시 보일러의 급수로 회수되는 것이 에너지와 물 소비 절약에서 유리하다. 따라서 보일러를 보유하고 있는 현장에서는 가능하면 응축수의 회수율을 높이고자 한다.The steam generated from the industrial boiler used for process heat exchange and power generation is advantageous in saving energy and water consumption by being condensed after being used and then returned to the boiler water supply. Therefore, in the field where the boiler is located, the recovery rate of the condensate should be increased as much as possible.
그런데 이 응축수가 발생하는 열 교환기 및 응축라인에는 보일러의 계통수에 포함되어 있는 탄산나트륨, 중산탄나트륨의 열분해로 인해 발생하는 이산화탄소가 스팀과 함께 이동하여 응축수에 용존 되면서 응축수의 전체적인 pH를 떨어트리게 된다. 또한 앞의 카보히드라지드의 경우 반응에 따른 부산물로서 이산화탄소가 발생되므로 이를 낮출 수 있는 별도의 방안이 필요하다.However, in the heat exchanger and condensation line where the condensate is generated, the carbon dioxide generated due to pyrolysis of sodium carbonate and sodium borate contained in the boiler system water moves together with steam and is dissolved in the condensed water, thereby lowering the overall pH of the condensed water . Further, in the case of the above-mentioned carbohydrazide, carbon dioxide is generated as a by-product of the reaction. Therefore, a separate method for lowering it is needed.
통상적으로 10kgf/㎠ 이하 보일러의 경우 보일러수의 pH는 11~11.8 사이로 유지하는 것이 부식 장애를 방지할 수 있는데 유리하다. 그러나 상기와 같이 이산화탄소의 유입으로 인해 pH가 떨어질 경우 바람직하지 않은 현상이 발생할 수 있다. 그러나 pH가 9 초과일 경우 금속에 부정적인 영향이 나타나는 것으로도 보고가 있었다.Generally, it is advantageous to keep the pH of the boiler water between 11 and 11.8 in the case of boilers below 10kgf / ㎠ to prevent corrosion trouble. However, undesirable phenomenon may occur when the pH is lowered due to the inflow of carbon dioxide as described above. However, it has been reported that when the pH is more than 9, the metal has a negative effect.
이와 같은 현상에 의해서 발생하는 부식을 이산화탄소 부식이라고 하는데, 이산화탄소 부식에 장기간 노출될 경우 강철 재질 뿐만 아니라 동합금 재질에 매우 치명적인 결과를 초래하여 심한 경우 열교환기가 파열되는 경우도 발생한다. 또한 디에틸히드록실아민과 산소와의 반응에 의해서 아세트산이 발생하며 이로 인해서 pH가 낮아지며 보일러 계통에 좋지 않은 영향을 미친다.Corrosion caused by this phenomenon is referred to as carbon dioxide corrosion, and if exposed to carbon dioxide corrosion for a long time, it will lead to a very lethal consequence to the material of the copper alloy as well as the steel material, and in some cases, the heat exchanger ruptures in severe cases. In addition, acetic acid is generated by the reaction of diethylhydroxylamine with oxygen, which lowers the pH and adversely affects the boiler system.
한편, 탈산소재로 황산나트륨, 하이드라진 이외에 탄닌(Tannin) 또는 탄닌산이 사용되어 왔으나, 현재에는 탈산소제로서의 환원작용이 약하고 보일러수를 착색시키는 문제로 인하여 식품공장 등, 안정성을 고려한 인체와 밀접한 개소에서 주로 적용하고 있다.On the other hand, tannin or tannic acid has been used in addition to sodium sulfate and hydrazine as a deoxidizing material. However, due to the problem that the reducing action as an oxygen scavenger is weak and the boiler water is colored, there is a problem in that, And the like.
최근 들어서 환경과 인체에 미치는 영향을 최소로 하는 탈산제에 대한 관심이 높아짐에 따라서 탄닌을 탈산제로서 다시 활용하고자 하는 요구가 있다. 탄닌산이 물에 대한 용해도가 2850g/Liter로 높고 인체에 대한 독성이 낮지만, 분자량이 높고 또한 알칼리 상에서 금속, 특히 철과 결합하여 철에 피막을 형성하므로 고온의 보일러 등에서 사용하기가 적절하지 않다. 특히 하기에서 언급하고 있는 헥사메틸렌테트라아민(Hexamethylenetetramine)이 아민 계통의 물질이기 때문에 이들과의 조합과는 적절하지 않을 수 있다.Recently, there is a demand for reusing tannin as a deoxidizing agent as interest in deoxidizing agents that minimize the environmental and human influence is increased. Although tannic acid has a high solubility in water of 2850 g / Liter and low toxicity to human body, it is not suitable for use in high temperature boiler because it has a high molecular weight and forms a film on iron in combination with metal, especially iron, on alkali. Especially, since hexamethylenetetramine mentioned below is an amine-based substance, combination with these may not be appropriate.
또 다른 탈산제의 문제로는 특별히 산소의 포화 정도를 바로 알 수 없고, 이온측정기 등을 통해서만 알 수 있다는 단점이 있다.Another disadvantage of the deoxidizer is that it can not know the degree of saturation of oxygen in particular and can only be known through an ion meter or the like.
본 발명에서는 용존 산소에 의한 부식은 물론 이산화탄소 부식을 동시에 해결하고 향후 환경 규제에 대비하여 독성이 낮은 발전소 보일러 수처리제 조성물을 제공하고 한다. 또한 인체에 해가 적으면서, 산소와의 결합력이 좋을 뿐만 아니라 산소 농도가 높아질 경우 색조가 변하여 육안으로도 쉽게 식별이 가능한 탈산제 조성물을 제공하고자 한다.The present invention provides a water treatment composition for a boiler of a power plant that solves carbon dioxide corrosion as well as corrosion by dissolved oxygen, and is low in toxicity in preparation for future environmental regulations. The present invention also provides a deoxidizing composition which can be easily visually distinguished by changing the color tone when oxygen concentration is high as well as having a good binding force with oxygen while reducing harm to the human body.
본 발명의 제1양태는 카보히드라지드(Carbohydrazide) 헥사메틸렌테트라아민(Hexamethylenetetramine, 이하 헥사민), 파이로갈릭산(Pyrogallic acid)을 유효성분으로 포함하는 발전소 보일러 수처리 조성물을 제공한다.A first aspect of the present invention provides a power plant boiler water treatment composition comprising Carbohydrazide, Hexamethylenetetramine (hereinafter, referred to as hexamine), and Pyrogallic acid as an active ingredient.
본 발명의 제2양태는 유효성분으로 디에틸히드록실아민(Diethyl Hydroxylamine, DEHA), 모르폴린(Morpholine)을 추가적으로 포함하는 것을 특징으로 하는 발전소 수처리 조성물을 제공한다.The second aspect of the present invention provides a water treatment composition for power plants, which further comprises diethylhydroxylamine (DEHA) and morpholine as an active ingredient.
본 발명의 제3양태는 카보히드라지드(Carbohydrazide) 0.1~10중량부; 헥사메틸렌테트라아민(Hexamethylenetetramine) 0.1~20중량부; 파이로갈릭산(Pyrogallic acid) 0.1~5중량부; 스케일방지제, 부식억제제, pH 조정제, 킬레이트제를 포함하는 첨가제 0.1~10중량부; 물 60~99.7중량부로 이루어진 발전소 보일러 수처리제 조성물을 발전소 보일러에 적용시 90℃ 이상의 계통수에서 카보히드라지드(Carbohydrazide)가 0.05∼5ppm으로 유지되고, 헥사메틸렌테트라아민이 0.2∼15ppm, 파이로갈릭산(Pyrogallic acid)이 0.2~15ppm으로 유지되는 것을 특징으로 하는 발전소 보일러 수처리계의 부식억제방법을 제공한다.A third aspect of the present invention is a pharmaceutical composition comprising 0.1 to 10 parts by weight of carbohydrazide; 0.1 to 20 parts by weight of hexamethylenetetramine; 0.1-5 parts by weight of pyrogallic acid; 0.1 to 10 parts by weight of an additive including a scale inhibitor, a corrosion inhibitor, a pH adjuster, and a chelating agent; When the water boiler composition of a power plant boiler comprising 60 to 99.7 parts by weight of water is applied to a boiler of a power plant, the carbohydrazide is maintained at 0.05 to 5 ppm in the system water of 90 ° C or more, 0.2 to 15 ppm of hexamethylenetetraamine, Pyrogallic acid) is maintained at 0.2 to 15 ppm. The present invention also provides a method for inhibiting corrosion of a boiler water treatment system of a power plant.
본 발명의 제4양태는 디에틸히드록실아민(Diethyl Hydroxylamine, DEHA), 모르폴린(Morpholine)을 추가적으로 포함하는 것을 특징으로 하는 발전소 보일러 수처리계의 부식억제방법을 제공한다.The fourth aspect of the present invention provides a corrosion inhibiting method of a power plant boiler water treatment system, which further comprises diethylhydroxylamine (DEHA) and morpholine.
이하 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 유효한 탈산소제로서 카보히드라지드(Carbohydrazide)를 사용한다. 카보히드라지드는 85℃까지는 히드라진보다 용존 산소 제거 속도가 높은 것으로 알려져 있으며, 150℃까지는 가수분해되어 히드라진과 이산화탄소를 생성하며, 200℃ 이상에서는 암모니아, 질소, 수소로 분해된다. 그러나 카보히드라지드는 히드라진과 달리 발암 물질로 인식되지 않고, 히드라진에 비해서 독성도 낮은 것으로 알려져 있다.The present invention uses Carbohydrazide as an effective deoxygenating agent. Carbohydrazide is known to have a higher dissolved oxygen removal rate than hydrazine up to 85 ° C. It hydrolyzes to 150 ° C to generate hydrazine and carbon dioxide, and decomposes to ammonia, nitrogen and hydrogen at temperatures above 200 ° C. Unlike hydrazine, however, carbohydrazide is not recognized as a carcinogen and is less toxic than hydrazine.
(H2N-NH)2CO + 2O2 → 2N2 + 3H2O + CO2 (H 2 N-NH) 2 CO + 2O 2 → 2N 2 + 3H 2 O + CO 2
통상적으로 카보히드라지드는 보일러 계통수에서 0.7ppm일 경우 산소제거의 효과가 뛰어난 것으로 알려져 있다.It is generally known that carbohydrazide has excellent oxygen removal effect when it is 0.7 ppm in the boiler system water.
통상적으로 용존 산소에 의한 부식 및 이산화탄소 부식, 낮아진 pH를 높이기 위해서 아민 계통의 물질이 사용된다. 또한 크롬산염, 아질산염, 몰리브덴산염, 중합인산염, 정인산염, 유기인산염, 아연염, 트리플루오로테노일아세톤, 염화벤제토늄, 2-메르캅토티아졸 등의 부식방지제 등이 사용된다.Typically, amine-based materials are used to increase corrosion and carbon dioxide corrosion by dissolved oxygen and lowered pH. In addition, corrosion inhibitors such as chromates, nitrites, molybdates, polymeric phosphates, phosphates, organic phosphates, zinc salts, trifluorothenoyl acetone, benzethonium chloride and 2-mercaptothiazole are used.
추가의 첨가제로서 인산, 폴리아크릴산, 폴리말레인산, 에틸렌디아민테트라아세트산, 아크릴레이트계 중합체, 디에틸렌 트리아민 펜타메틸렌 포스포닉산 등의 스케일 방지제, 수산화나트륨, 수산화칼륨, 탄산나트륨, 제3인산나트륨, 제1인산나트륨, 제1인산칼륨, 제2인산칼륨, 제3인산칼륨, 헥사메타인산나트륨, 트리폴리인산나트륨, 포타슘소르베이트 등의 pH 조정제도 사용될 수 있다.As a further additive, an anti-scale agent such as phosphoric acid, polyacrylic acid, polymaleic acid, ethylenediaminetetraacetic acid, acrylate-based polymer, diethylenetriaminepentamethylenephosphonic acid and the like, or an antioxidant such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium tertiary phosphate PH adjustment systems such as sodium monophosphate, potassium monophosphate, potassium dibasic potassium phosphate, potassium dihydrogenphosphate, sodium hexametaphosphate, sodium tripolyphosphate, and potassium sorbate may be used.
헥사메틸렌테트라아민 (Hexamethylenetetramine)은 아래 구조와 같은 격자 구조를 가지고 있는 화합물로서 물에 쉽게 녹는다. 헥사메틸렌테트라아민은 간단하게 헥사민이라고도 불리며 소량인 경우 체내 복용이 가능하며 비뇨기 소염제로써 의약품 제조에도 사용될 만큼 크게 독성이 없는 물질이고 가격도 저렴하며 구입이 용이한 장점이 있다. 종래 탈산제에서 사용하고 있는 아민 화합물인 디에틸히드록실아민, 싸이클로헥실아민, 디메틸아미노프로필아민 등의 아민은 1차 또는 2차 아민으로서 4차 아민인 헥사메틸렌테트라아민과 아민의 종류에서도 크게 차이가 날 뿐만 아니라 헥사메틸렌테트라아민과 녹는점 280℃, 플리쉬 포인트 250℃보다도 훨씬 낮은 값을 가지고 있다. 이로 인해서 훨씬 더 높은 휘발성을 가지고 있어, 탈산제로서 계속적인 보충이 필요하다는 단점이 있다.Hexamethylenetetramine (Hexamethylenetetramine) is a compound having a lattice structure as shown below and easily dissolves in water. Hexamethylenetetraamine is also known as hexamine, and it can be taken in the body if it is a small amount, and it is a urine antiinflammatory agent, which is not toxic enough to be used for the manufacture of medicines, and is cheap and easy to purchase. Amines such as diethylhydroxylamine, cyclohexylamine, and dimethylaminopropylamine, which are amine compounds used in deoxidizers in the past, differ greatly in the types of hexamethylenetetramines and amines, which are quaternary amines as primary or secondary amines Not only the blade, but also hexamethylenetetramine, has a melting point far lower than 280 ° C and flip point of 250 ° C. As a result, it has a much higher volatility and has a disadvantage of requiring continuous replenishment as a deoxidizer.
물에 용해된 이산화탄소는 탄산염 상태로 부식에 관여하며 아민 계통의 물질은 아래와 같은 반응을 통해 탄산염의 부식을 억제하면서 pH를 높인다.Carbon dioxide dissolved in water is in the form of carbonate, which is involved in corrosion. Amine-based materials increase the pH while suppressing the corrosion of carbonate through the following reaction.
R-NH2 + H2O → R-NH3 + + OH- R - NH 2 + H 2 O -> R - NH 3 + + OH -
R-NH3 + + OH- + H2CO3 → R-NH3 + + HCO3 - + H2OR - NH 3 + + OH - + H 2 CO 3 - > R - NH 3 + + HCO 3 - + H 2 O
비특허문헌 2에서는 헥사메틸렌테트라아민만을 사용하여 응축수에서 이산화탄소에 의한 부식 방지를 연구하였으며 헥사메틸렌테트라아민이 이에 대해서 효과가 있는 것으로 밝혀졌다. 또한 헥사메틸렌테트라아민이 승화성이 있기 때문에 탈기기 이후에 투입되어야 하는 것으로 기재하고 있다. 그러나, 상기 연구논문은 탈산제제에 대해서는 전혀 언급을 하지 않고 있으며 이에 대한 조합 등을 시사하고 있지 않을 뿐만 아니라 실시예도 기재하고 있지 않다.In non-patent document 2, only corrosion inhibition by carbon dioxide in condensed water was studied using hexamethylenetetramine, and hexamethylenetetramine was found to be effective against this. Further, it is described that hexamethylenetetramine should be added after deaerating because of its sublimation properties. However, the above-mentioned research article does not mention the deoxidizing agent at all and does not suggest a combination thereof, nor does it describe the embodiment.
통상적으로 헥사민은 보일러 계통수에서 3~5ppm일 경우 이산화탄소 제거의 효과가 뛰어난 것으로 알려져 있다.Typically, hexamine is known to excel in the removal of carbon dioxide when it is 3 to 5 ppm in boiler water.
본 발명에서 독성이 적은 카보히드라지드가 탈산제제로서 역할을 하지만 반대로 이산화탄소를 발생시키는 점에 착안하여 이산화탄소를 제거할 수 있으면서 또한 독성이 적고 가격이 저렴하면서도 입수가 쉬운 헥사메틸렌테트라아민을 부가한 카보히드라지드(Carbohydrazide), 헥사메틸렌테트라아민(Hexamethylenetetramine), 파이로갈릭산(Pyrogallic acid)을 유효성분으로 포함하는 발전소 보일러 수처리제 조성물 및 이를 이용한 발전소 보일러 수처리계 부식억제방법을 제공하고자 한다.In the present invention, carbohydrazide having a low toxicity serves as a deoxidizing agent, but on the contrary, it is possible to remove carbon dioxide by taking into consideration the fact that carbon dioxide is generated, and also to provide a carbohydrate with a hexamethylenetetraamine added with low toxicity, The present invention provides a water treatment composition for a boiler of a power plant including Carbohydrazide, Hexamethylenetetramine and Pyrogallic acid as active ingredients, and a method for inhibiting corrosion of a boiler water treatment system using the same.
한편 파이로갈릭산은 하기와 같은 식의 화합물이다. 통상적으로 파이로갈릭산은 산소를 흡수할 경우 갈색으로 변하는 성질로 인해서 염색약, 과거 흑백 사진의 현상액으로 사용되었다.On the other hand, pyrogallic acid is a compound of the following formula. Traditionally, pyrogalic acid has been used as a developer for dyeing medicines, past black and white photographs due to its brown nature when it absorbs oxygen.
파이로갈릭산은 물에 대한 용해도가 높기 때문에 용해된 상태로 사용될 수 있으며, 특히 알칼리 용액에서 산소를 흡수하여 갈색으로 변하는 특징이 있다. 그러나 이상과 같은 특징을 탈산제에 적용한 경우는 전혀 없었다. 통상적으로 사용하는 온도 또한 본 발명과 같이 고온에서 적용된 경우가 없다.Pyrogallic acid can be used in a dissolved state because of its high solubility in water. In particular, it has a characteristic of absorbing oxygen and changing to brown in alkaline solution. However, none of the above features have been applied to deoxidizers at all. A temperature usually used is not applied at a high temperature as in the present invention.
특히 산소를 흡수하여 갈색으로 변색하기 위해서는 알칼리 성을 띄어야 하는데, 본 발명에서 사용되는 인체에 독성이 미약한 헥사민은 4차 아민으로서 파이로갈릭산의 용도를 높일 수 있는 알칼리성을 제공할 수 있으며, 이러한 조합을 통해서 본 발명은 산소, 이산화탄소 부식, 및 파이로갈릭산에 의한 추가의 산소 제거 및 산소의 흡수 정도에 따른 변색을 통해서 탈산제의 포화 정도를 가늠할 수 있는 효과가 있다. 아래 실시예는 본 출원인에 의한 선행특허에서 실시된 실시예와 동일한 것으로서 본원에서 추가한 파이로갈릭산을 부가하였을 경우, 초기에는 무색을 띄다가 산소의 흡수가 늘어남에 따라 미약한 갈색이 발현되는 것을 알 수 있었다. 또한 헥사민을 부여하지 않은 경우에는 갈색의 거의 나타나지 않음을 알 수 있었다.Particularly, in order to absorb oxygen and change to brown color, it must be alkaline. Hexamine, which is weakly toxic to the human body used in the present invention, can provide alkalinity that can increase the use of pyrogallic acid as a quaternary amine Through such a combination, the present invention has an effect of gauging the degree of saturation of the deoxidizing agent through oxygen, carbon dioxide corrosion, and discoloration depending on the degree of oxygen addition and oxygen absorption by pyrogallic acid. The following examples are the same as the examples of the prior patent of the applicant of the present invention. When pyrogallic acid added herein is added, it is colorless at the beginning, and weak brown is expressed as absorption of oxygen increases . It was also found that almost no brown color was observed when hexamine was not added.
본 발명에 따른 조성물 및 방법은 용존 산소에 의한 부식은 물론 이산화탄소 부식을 동시에 해결하고 향후 환경 규제에 대비하여 독성이 낮은 효과가 있다. 또한 사용되는 물질이 경제적이며 쉽게 구할 수 있는 장점이 있다. 또한 산소의 흡수에 따라 눈으로 관측이 가능하다는 장점이 있다.The composition and method according to the present invention are effective in solving carbon dioxide corrosion as well as corrosion by dissolved oxygen, and have low toxicity in preparation for environmental regulation in the future. Also, the materials used are economical and readily available. It also has the advantage that it can be observed with the eye according to the absorption of oxygen.
도 1은 파이로갈릭산이 포함된 용액의 변색 정도를 감별하기 위한 기준을 위한 조성물의 변화를 나타낸다.BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the compositional change for the criteria for discriminating the degree of discoloration of solutions containing pyrogallic acid.
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 예시적으로 설명하기 위한 것으로 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
<실시예><Examples>
<색깔의 기준 설정><Color reference setting>
파이로갈릭산이 포함되었을 경우 조성물의 색 변화에 대한 기준을 세우기 위해서 파이로갈릭산과 다른 화합물을 포함한 다양한 조성물을 제조하였다. 도 1은 농도에 따른 조성물의 색깔 변화를 보여주고 있다. 가장 왼쪽의 증류수를 기준인 '0'으로 하였고, 몰포린과 파이로갈릭산이 혼합된 용액(가장 오른쪽)에 대해는 '15'를 기준으로 하였다. 상기 색을 기준으로 대비하여 짙어진 정도를 수치화하였다.Various compositions including pyrogallic acid and other compounds were prepared to establish the criteria for color change of the composition when pyrogallic acid was included. Figure 1 shows the color change of the composition according to the concentration. The leftmost distilled water was set to '0', and the solution containing the molarin and pyrogallic acid (rightmost) was based on '15'. The degree of darkening in comparison with the above color was quantified.
<사용된 화합물>≪ Compound used >
증류수는 역삼투압을 이용한 증류수 제조장치를 사용하였으며 분석에 사용된 화학약품은 아래와 같은 순도를 가지고 있다.The distilled water used was a distilled water production apparatus using reverse osmosis pressure. The chemical used in the analysis had the following purity.
농도에 따른 아래의 탈산소제 등의 조성물에 증류수를 부가하여 총 100g의 용액을 만든 후 색상을 관측하였다. 온도는 상온(22℃), 상압에서 진행하였다.Distilled water was added to the composition such as the following deoxidizer according to the concentration to make a total of 100 g of solution, and the color was observed. The temperature was maintained at room temperature (22 ° C) and normal pressure.
Pyrogallic acid +
증류수Carbohydrazide +
Pyrogallic acid +
Distilled water
2.5g
97.0g0.5 g
2.5 g
97.0 g
2.5g
96.5g1.0 g
2.5 g
96.5 g
2.5g
92.5g5.0g
2.5 g
92.5 g
Pyrogallic acid +
증류수Carbohydrazide + Hexamethylenetetramine +
Pyrogallic acid +
Distilled water
0.05g
2.5g
96.95g0.5 g
0.05 g
2.5 g
96.95 g
0.05g
2.5g
96.45g1.0 g
0.05 g
2.5 g
96.45 g
0.05g
2.5g
92.45g5.0g
0.05 g
2.5 g
92.45g
상기 1, 2 조성물 모두 카보히드라지드의 농도가 높아짐에 따라 용액의 색이 옅어지는 것을 알 수 있었다. 본원 발명에 따른 조성물은 이와 같이 용존 산소 등의 변화를 육안으로 바로 관측이 가능하다는 장점이 있다.It was found that the color of the solution became thinner as the concentration of the carbohydrazide was increased in both the compositions 1 and 2. The composition according to the present invention has such an advantage that the change of dissolved oxygen and the like can be directly observed with the naked eye.
Claims (4)
유효성분으로 디에틸히드록실아민(Diethyl Hydroxylamine, DEHA), 모르폴린(Morpholine)을 추가적으로 포함하는 것을 특징으로 하는 발전소 수처리 조성물.The method according to claim 1,
And further comprising diethylhydroxylamine (DEHA) and morpholine as an effective ingredient.
디에틸히드록실아민(Diethyl Hydroxylamine, DEHA), 모르폴린(Morpholine)을 추가적으로 포함하는 것을 특징으로 하는 발전소 보일러 수처리계의 부식억제방법.The method of claim 3,
A method for inhibiting corrosion of a boiler water treatment system of a power plant, which comprises additionally diethylhydroxylamine (DEHA) and morpholine.
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| KR100315496B1 (en) | 1997-08-13 | 2002-01-15 | 조민호 | Method for Inhibiting Corrosion of Boiler Condensation System Using Corrosion Inhibiting Composition |
| JP2012021215A (en) | 2010-07-16 | 2012-02-02 | Kurita Water Ind Ltd | Anticorrosive for boiler |
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| CN111018028B (en) * | 2019-12-06 | 2022-01-28 | 南通联膦化工有限公司 | Environment-friendly boiler deoxidant |
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