CN102642934B - A kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor and preparation and application thereof - Google Patents
A kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor and preparation and application thereof Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 72
- 230000007797 corrosion Effects 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 68
- 229910000975 Carbon steel Inorganic materials 0.000 title claims abstract description 41
- 239000010962 carbon steel Substances 0.000 title claims abstract description 41
- 239000003112 inhibitor Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000001816 cooling Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 7
- 239000010452 phosphate Substances 0.000 title abstract description 7
- -1 rare-earth salts Chemical class 0.000 claims abstract description 27
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 26
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 21
- 230000005764 inhibitory process Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims abstract description 17
- 229940050410 gluconate Drugs 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229960003975 potassium Drugs 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 241000532030 Menesia Species 0.000 claims description 8
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical group [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 claims description 8
- 239000004224 potassium gluconate Substances 0.000 claims description 8
- 235000013926 potassium gluconate Nutrition 0.000 claims description 8
- 229960003189 potassium gluconate Drugs 0.000 claims description 8
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical group [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 7
- 235000011478 zinc gluconate Nutrition 0.000 claims description 7
- 239000011670 zinc gluconate Substances 0.000 claims description 7
- 229960000306 zinc gluconate Drugs 0.000 claims description 7
- NEEHYRZPVYRGPP-IYEMJOQQSA-L calcium gluconate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEEHYRZPVYRGPP-IYEMJOQQSA-L 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 claims description 6
- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical compound [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 0.000 claims description 5
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 235000015598 salt intake Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 241000195493 Cryptophyta Species 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000026676 system process Effects 0.000 abstract description 2
- 230000009897 systematic effect Effects 0.000 abstract description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 22
- 238000004090 dissolution Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 235000005074 zinc chloride Nutrition 0.000 description 11
- 239000011592 zinc chloride Substances 0.000 description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- UOCLRXFKRLRMKV-UHFFFAOYSA-N trolnitrate phosphate Chemical compound OP(O)(O)=O.OP(O)(O)=O.[O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O UOCLRXFKRLRMKV-UHFFFAOYSA-N 0.000 description 2
- 229960001939 zinc chloride Drugs 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000012827 research and development Methods 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
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000013014 water-saving technology Methods 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor and preparation and application thereof, wherein composite corrosion inhibitor is by molybdate or tungstate, gluconate, rare-earth salts, and zinc salt, stablizer forms, for carbon steel difficult passive behavior in the seawater, and marine circulating cooling system process characteristic and systematic economy operating requirement, propose first to adopt the composite polynary prefilming agent of high density to process, the Recompounded multielement proceeding to lower concentration more normally runs the technique of inhibiter process, and then realize inhibiter high density fast filming, lower concentration maintains the object run and repair film, control corrosion of carbon steel speed and be less than 0.02mm/a, corrosion inhibition rate is greater than 98%.Corrosion inhibitor product raw material sources of the present invention are extensive, and solvability is good, and cost performance is high, belongs to low toxicity level Industrial products, not pollution of marine environment; Good with seawater dirt dispersion agent, bacterium algae inhibitor compatibleness.
Description
Technical field
The present invention relates to technology of industrial recirculating cooling water treatment field, more particularly, relate to a kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor and preparation and application thereof.
Background technology
Marine circulating cooling system is as an environmental protective, water saving technology; huge potential application demand is there is in electric power, chemical industry, petrochemical industry, iron and steel contour water consumption industry; exploitation and using of seawater replaces fresh water as industrial circulating cooling water, is to alleviate China coast city and regional Freshwater resources are in short supply, one of the important channel of the protection marine eco-environment.
In marine circulating cooling system system, the corrosion of seawater to metallic substance is the primary problem solved.No matter be at present economically or from processing consider, carbon steel is all one of preferred material, and suppresses corrosion of carbon steel by adding inhibiter, is not only simply but also cost-effective method.From the 1950's, large quantity research is carried out to the inhibition of seawater medium carbon steel both at home and abroad, mainly from the inhibition efficiency improving inhibiter, do not considered environmental issue.Based on the strategic thought of environment protection and Sustainable development, in 20 end of the centurys, along with the proposition of Green Chemistry concept and the development of marine circulating cooling system technology, the domestic carbon steel corrosion inhibitor research about seawater or simulated seawater is very active, achieves good progress.Such as: " a kind of novel corrosion inhibitor suppressing carbon steel to corrode in the seawater " (Chinese publication CN1224079A, 1999) the phosphorus system compound prescription be made up of 45% ~ 55% Sodium orthomolybdate, 25% ~ 35% nitranol, 15% ~ 25% primary zinc phosphate is provided, at 80ppm ~ 230ppm working concentration, its corrosion inhibition rate is close to 100%." a kind of suppress iron and steel to corrode in tap water or seawater inhibiter and using method " (Chinese granted patent CN101660162B, 2012) the phosphorus system compound prescription be made up of 20% ~ 40% nitranol, 20% ~ 40% primary zinc phosphate, 20% ~ 40% tripoly phosphate sodium STPP, 10% ~ 30% hexamethylenetetramine is provided, at 75ppm ~ 250ppm working concentration, its corrosion mitigating effect is excellent.
But in technology, economy, environmental protection, be still faced with some problem demanding prompt solutions: (1) experiment condition can not simulated seawater circulating cooling system operation condition (temperature, flow velocity, concentration rate etc.) very well, and the adaptability of achievement in research in cooled with seawater system does not have cogency; (2) neutralization technology index has much room for improvement, some the composite corrosion inhibitor corrosion mitigating effects developed still can, control corrosion of carbon steel speed substantially near the border of the 0.075mm/a of circularly-cooling sea water Treatment Design regulation and stipulation, inhibition overdose space is little; (3) cost of water treatment is higher, and inhibiter single dose or compound prescription in the seawater consumption are large, and as Sodium orthomolybdate or the huge height of sodium wolframate unit price, and working concentration is higher.And the mean level (ML) in the more existing industrial colling of some composite corrosion inhibitor ton cost of water treatment of preresearch estimates is up to several times and even tens times, use cost is very expensive, does not have practicality and the market competitiveness at salt water cooling system; (4) discharge water will limit by environmental protection, for a long time, the phosphorus of body eutrophication (phosphine) corrosion inhibitor is easily caused to occupy the main flow of water conditioner, in recent years, by the restriction of country, local sewage drainage standard and sea environment-friendly, the cry of " limit phosphorus ", " taboo phosphorus " has again been started in treatment of cooling water field, some phosphorous and difficult degradation water conditioners lose the competitive edge in market gradually, be faced with the situation be eliminated, without phosphorus water chemical treatment technology has become the focus that industry is paid close attention to.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art; a kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor and preparation and application thereof are provided; mainly for the needs that current marine circulating cooling system technical development and the marine eco-environment are protected, design the novel carbon steel corrosion inhibitor of sea water of research and development around performance, environment and economy three general objective.
Object of the present invention is achieved by following technical proposals:
A kind of circularly-cooling sea water non-phosphate environment-friendly type carbon steel composite corrosion inhibitor, the inhibiter that the prefilming agent used by pretreatment stage and normal operating phase use forms, wherein:
Described prefilming agent is made up of molybdate or tungstate, gluconate, rare-earth salts, zinc salt and stablizer, wherein:
Described molybdate is at least one in an alkali metal salt of molybdic acid, alkaline earth salt, ammonium molybdate, such as Sodium orthomolybdate, potassium molybdate, magnesium molybdate or ammonium molybdate, consumption is 50mg/L ~ 400mg/L, mainly utilizes the passivation precipitating action of molybdate to form protective membrane;
Described tungstate is at least one in an alkali metal salt of wolframic acid, ammonium tungstate, such as sodium wolframate, potassium wolframate or ammonium tungstate, and consumption is 50mg/L ~ 400mg/L, mainly utilizes the passivation precipitating action of tungstate to form protective membrane;
Described gluconate is an alkali metal salt or the alkaline earth salt of gluconic acid, such as Sunmorl N 60S, Potassium Gluconate, calglucon or Menesia, and consumption is 200mg/L ~ 500mg/L, mainly utilizes the adsorption precipitation effect of gluconate;
Described rare-earth salts is inorganic acid salt or the organic acid salt of rare earth element, be specially hydrochloride, nitrate or acetate, such as Lanthanum trichloride, lanthanum nitrate, lanthanum acetate, zirconium nitrate, Cerium II Chloride, cerous nitrate, cerous acetate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium, consumption is 400mg/L ~ 900mg/L, mainly utilizes rare earth element to react;
Described zinc salt is zinc sulfate, zinc chloride or Zinc Gluconate, and consumption is 50mg/L ~ 150mg/L, mainly utilizes zine ion to react;
Described stablizer is ethylenediamine tetraacetic acid (EDTA), hexamethylenetetramine or Sodium dodecylbenzene sulfonate, and consumption is 300mg/L ~ 600mg/L, utilizes it to cationic chelating and stably dispersing effect;
Described inhibiter for be made up of molybdate or tungstate, gluconate, rare-earth salts and zinc salt, wherein:
Described molybdate is at least one in an alkali metal salt of molybdic acid, alkaline earth salt, ammonium molybdate, such as Sodium orthomolybdate, potassium molybdate, magnesium molybdate or ammonium molybdate, and consumption is 1mg/L ~ 4mg/L, mainly utilizes the passivation precipitating action of molybdate to form protective membrane;
Described tungstate is at least one in an alkali metal salt of wolframic acid, ammonium tungstate, such as sodium wolframate, potassium wolframate or ammonium tungstate, and consumption is 1mg/L ~ 4mg/L, mainly utilizes the passivation precipitating action of tungstate to form protective membrane;
Described gluconate is an alkali metal salt or the alkaline earth salt of gluconic acid, such as Sunmorl N 60S, Potassium Gluconate, calglucon or Menesia, and consumption is 10mg/L ~ 30mg/L, mainly utilizes the adsorption precipitation effect of gluconate;
Described rare-earth salts is inorganic acid salt or the organic acid salt of rare earth element, be specially hydrochloride, nitrate or acetate, such as Lanthanum trichloride, lanthanum nitrate, lanthanum acetate, zirconium nitrate, Cerium II Chloride, cerous nitrate, cerous acetate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium, consumption is 5mg/L ~ 15mg/L, mainly utilizes rare earth element participate in and react;
Described zinc salt is zinc sulfate, zinc chloride or Zinc Gluconate, and consumption is that 1mg/L ~ 5mg/L is (with Zn
2+meter), mainly utilize zine ion to react.
Each component content is preferably as follows:
In the prefilming agent that described pretreatment stage uses
Described molybdate consumption is 100mg/L ~ 300mg/L
Described tungstate consumption is 100mg/L ~ 300mg/L
Described gluconate consumption is 300mg/L ~ 500mg/L
Described rare-earth salts consumption is 500mg/L ~ 800mg/L
Described zinc salt consumption is 80mg/L ~ 150mg/L
Described stabilizing agent dosage is 350mg/L ~ 550mg/L
In the inhibiter that described normal operating phase uses
Described molybdate consumption is 1.5mg/L ~ 3mg/L
Described tungstate consumption is 2mg/L ~ 4mg/L
Described gluconate consumption is 10mg/L ~ 25mg/L;
Described rare-earth salts consumption is 5mg/L ~ 10mg/L
Described zinc salt consumption is (with Zn
2+meter) be 1.5mg/L ~ 4mg/L
When being prepared composite corrosion inhibitor of the present invention, constant volume is carried out after utilizing solvent (deionized water or tap water) directly to dissolve corresponding material, can to reach finite concentration (can utilize to stir or heat and carry out accelerate dissolution), then its usage quantity is calculated according to seawater usage quantity and the strength of solution prepared, by the solution prepared and sea water mixing, with the concentration requirement making each component in final seawater reach inhibiter under prefilming agent and normal operation respectively.
Composite corrosion inhibitor of the present invention selects without phosphorus, environmentally friendly inorganic salt, organic salt and rare-earth salts compound to be raw material, the effect of each component collaborative, by the cathode type binding mode of inorganic salt precipitation membrane, organic salt adsorption film and rare-earth salts, zinc salt, realize for carbon steel corrosion inhibition in the seawater.
In use, first the prefilming agent that pretreatment stage uses that is used for of preparation to be added in seawater or supplementary seawater and to make each component in final seawater reach the concentration requirement of prefilming agent respectively by (step 1), then normal temperature (15 DEG C ~ 35 DEG C, preferably 20 DEG C ~ 30 DEG C) under, rotating speed 80r/min ~ 120r/min or start recycle pump condition under, continuous operation at least 24h, preferred 24h ~ 48h, to form preservative protective film fast at steel surface; After pre-film, (step 2) proceeds in normal inhibition seawater; the inhibiter that the normal operating phase being about to preparation uses to be added in seawater or cooling system and to make each component final reach the concentration requirement of inhibiter under normal operation respectively, maintains inhibiter lower concentration and runs with the reparation realized protective membrane.
Composite corrosion inhibitor of the present invention is by molybdate or tungstate, gluconate, rare-earth salts, and zinc salt, stablizer forms, for carbon steel difficult passive behavior in the seawater, and marine circulating cooling system process characteristic and systematic economy operating requirement, after proposing first to adopt the Recompounded multielement prefilming agent of high density to process, the Recompounded multielement proceeding to lower concentration more normally runs the technique of inhibiter process, and then realize inhibiter high density fast filming, lower concentration maintains the object run and repair film, control corrosion of carbon steel speed and be less than 0.02mm/a, corrosion inhibition rate is greater than 98%, the 0.075mm/a standard specification that technical performance index is much better than " circularly-cooling sea water Treatment Design specification " (GB/T 23248-2009) specifies, technico-economical comparison can reach the domestic marine circulating cooling system demonstration project level now run substantially.Corrosion inhibitor product raw material sources of the present invention are extensive, and solvability is good, and cost performance is high, belongs to low toxicity level Industrial products, not pollution of marine environment; Good with seawater dirt dispersion agent, bacterium algae inhibitor compatibleness, be a kind of efficient, economic non-phosphate environment-friendly type seawater water conditioner.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.The seawater used takes from Tianjin seismic network seawater cleaning factory, water-quality guideline: pH value 7.31, specific conductivity 3.99 × 10
4μ s/cm, basicity 123mg/L, turbidity < 10mg/L, Ca
2+380mg/L, Mg
2+1162mg/L, SO
4 2-2478mg/L, Cl
-17403mg/L.
Corrosion weight loss method is according to " mensuration-rotary hanging plate method of water conditioner corrosion inhibition " GB/T 18175-2000 standard; material is common standard A3 carbon steel (50mm × 25mm × 2mm); experiment condition is: after the pre-film 48h of normal temperature dynamic (rotating speed 80r/min); proceed in the normal inhibition seawater of 50 DEG C ± 1 DEG C, run 72 hours continuously.Electrochemical method adopts AC impedence method, and test frequency 100KHz ~ 10mHz, applies AC signal under open circuit potential, and voltage magnitude is ± 10mV.
Embodiment 1
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain Sodium orthomolybdate 200mg/L, Sunmorl N 60S 200mg/L, Cerium II Chloride 400mg/L, ethylenediamine tetraacetic acid (EDTA) 400mg/L, zinc chloride 150mg/L, under normal temperature (15 DEG C) rotating speed 80r/min, run 24 hours (i.e. carbon steel electrode film forming 24h) continuously, then measuring polarization resistance is 16400 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain Sodium orthomolybdate 1.5mg/L, Sunmorl N 60S 20mg/L, Cerium II Chloride 10mg/L, zinc chloride (Zn
2+meter) 1mg/L, maintain lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0193mm/a, corrosion inhibition rate 98.07% simultaneously.
Embodiment 2
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain Sodium orthomolybdate 400mg/L, Potassium Gluconate 300mg/L, cerous acetate 500mg/L, ethylenediamine tetraacetic acid (EDTA) 500mg/L, Zinc Gluconate 140mg/L, adds in seawater, under normal temperature (35 DEG C) rotating speed 120r/min, continuous operation 48 hours (i.e. carbon steel electrode film forming 48h), then measuring polarization resistance is 28300 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain ammonium molybdate 1mg/L, Menesia 10mg/L, Yttrium trinitrate 15mg/L, zinc sulfate (Zn
2+meter) 5mg/L, drops in seawater, maintains lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0164mm/a, corrosion inhibition rate 98.36% simultaneously.
Embodiment 3
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain sodium wolframate 250mg/L, Potassium Gluconate 500mg/L, lanthanum nitrate 800mg/L, Sodium dodecylbenzene sulfonate 300mg/L, zinc chloride 50mg/L, adds in seawater, under normal temperature (25 DEG C) rotating speed 100r/min, continuous operation 30 hours (i.e. carbon steel electrode film forming 30h), then measuring polarization resistance is 21100 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain Sodium orthomolybdate 4mg/L, Sunmorl N 60S 30mg/L, cerous nitrate 5mg/L, zinc chloride (Zn
2+meter) 4mg/L, drops in seawater, maintains lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0188mm/a, corrosion inhibition rate 98.12% simultaneously.
Embodiment 4
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain potassium wolframate 250mg/L, Menesia 400mg/L, cerous nitrate 900mg/L, hexamethylenetetramine 600mg/L, zinc chloride 70mg/L, adds in seawater, under normal temperature (20 DEG C) rotating speed 120r/min, continuous operation 36 hours (i.e. carbon steel electrode film forming 36h), then measuring polarization resistance is 18700 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain sodium wolframate 2mg/L, Sunmorl N 60S 25mg/L, lanthanum nitrate 10mg/L, zinc sulfate (Zn
2+meter) 1.5mg/L, drops in seawater, maintains lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0189mm/a, corrosion inhibition rate 98.11% simultaneously.
Embodiment 5
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain potassium wolframate 250mg/L, Sunmorl N 60S 400mg/L, Yttrium trichloride 550mg/L, ethylenediamine tetraacetic acid (EDTA) 350mg/L, zinc chloride 80mg/L, adds in seawater, under normal temperature (30 DEG C) rotating speed 100r/min, continuous operation 40 hours (i.e. carbon steel electrode film forming 40h), then measuring polarization resistance is 17900 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain ammonium tungstate 2mg/L, Sunmorl N 60S 15mg/L, Yttrium trinitrate 8mg/L, zinc chloride (Zn
2+meter) 3mg/L, drops in seawater, maintains lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0135mm/a, corrosion inhibition rate 98.31% simultaneously.
Embodiment 6
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain ammonium tungstate 400mg/L, Potassium Gluconate 300mg/L, Lanthanum trichloride 400mg/L, hexamethylenetetramine 600mg/L, zinc chloride 150mg/L, adds in seawater, under normal temperature (20 DEG C) rotating speed 80r/min, continuous operation 30 hours (i.e. carbon steel electrode film forming 30h), then measuring polarization resistance is 17700 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain ammonium tungstate 2mg/L, Sunmorl N 60S 25mg/L, Cerium II Chloride 15mg/L, zinc chloride (Zn
2+meter) 1.5mg/L, drops in seawater, maintains lower concentration and run to realize the reparation that standard carbon steel corrosion coupon is protected, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0171mm/a, corrosion inhibition rate 98.29% simultaneously.
Embodiment 7
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain potassium wolframate 400mg/L, calglucon 350mg/L, zirconium nitrate 500mg/L, ethylenediamine tetraacetic acid (EDTA) 500mg/L, zinc sulfate 150mg/L, adds in seawater, under normal temperature (20 DEG C) rotating speed 120r/min, continuous operation 24 hours (i.e. carbon steel electrode film forming 24h), then measuring polarization resistance is 15400 Ω cm
2.
With constant volume after the corresponding material of deionized water dissolving, utilize stirring to carry out accelerate dissolution simultaneously, be added in seawater and make it contain potassium wolframate 4mg/L, Menesia 20mg/L, zirconium nitrate 15mg/L, Zinc Gluconate (Zn
2+meter) 5mg/L, drops in seawater, maintains lower concentration and run with the reparation realized standard carbon steel corrosion coupon upper protective film, carry out corrosion weight loss test, known corrosion of carbon steel speed 0.0162mm/a, corrosion inhibition rate 98.54% simultaneously.
Although be described the preferred embodiments of the present invention above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; do not departing under the ambit that present inventive concept and claim protect, can also make the concrete conversion of a lot of form, these all belong within protection scope of the present invention.
Claims (9)
1. the without phosphorus carbon steel composite corrosion inhibitor of circularly-cooling sea water, the inhibiter that the prefilming agent used by pretreatment stage and normal operating phase use forms, it is characterized in that, described prefilming agent is made up of molybdate or tungstate, gluconate, rare-earth salts, zinc salt and stablizer, wherein:
Described molybdate is potassium molybdate or magnesium molybdate, and consumption is 50mg/L ~ 400mg/L;
Described tungstate is potassium wolframate or ammonium tungstate, and consumption is 50mg/L ~ 400mg/L;
Described gluconate is Potassium Gluconate, calglucon or Menesia, and consumption is 200mg/L ~ 500mg/L;
Described rare-earth salts is zirconium nitrate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium, and consumption is 400mg/L ~ 900mg/L;
Described zinc salt is Zinc Gluconate, and consumption is 50mg/L ~ 150mg/L;
Described stablizer is hexamethylenetetramine or Sodium dodecylbenzene sulfonate, and consumption is 300mg/L ~ 600mg/L;
The inhibiter that described normal operating phase uses for be made up of molybdate or tungstate, gluconate, rare-earth salts and zinc salt, wherein:
Described molybdate is potassium molybdate or magnesium molybdate, and consumption is 1mg/L ~ 4mg/L;
Described tungstate is potassium wolframate or ammonium tungstate, and consumption is 1mg/L ~ 4mg/L;
Described gluconate is Potassium Gluconate, calglucon or Menesia, and consumption is 10mg/L ~ 30mg/L;
Described rare-earth salts is zirconium nitrate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium, and consumption is 5mg/L ~ 15mg/L;
Described zinc salt is Zinc Gluconate, with Zn
2+meter consumption is 1mg/L ~ 5mg/L.
2. the without phosphorus carbon steel composite corrosion inhibitor of a kind of circularly-cooling sea water according to claim 1, it is characterized in that, each component content is preferably as follows:
In the prefilming agent that described pretreatment stage uses, described molybdate consumption is 100mg/L ~ 300mg/L; Described tungstate consumption is 100mg/L ~ 300mg/L; Described gluconate consumption is 300mg/L ~ 500mg/L; Described rare-earth salts consumption is 500mg/L ~ 800mg/L; Described zinc salt consumption is 80mg/L ~ 150mg/L; Described stabilizing agent dosage is 350mg/L ~ 550mg/L;
In the inhibiter that described normal operating phase uses, described molybdate consumption is 1.5mg/L ~ 3mg/L; Described tungstate consumption is 2mg/L ~ 4mg/L; Described gluconate consumption is 10mg/L ~ 25mg/L; Described rare-earth salts consumption is 5mg/L ~ 10mg/L; Described zinc salt consumption is 1.5mg/L ~ 4mg/L, with Zn
2+meter.
3. prepare the method for composite corrosion inhibitor as claimed in claim 1 for one kind, it is characterized in that, constant volume is carried out after utilizing solvent directly to dissolve corresponding material, to reach finite concentration, then its usage quantity is calculated according to seawater usage quantity and the strength of solution prepared, by the solution prepared and sea water mixing, with the concentration requirement making each component in final seawater reach inhibiter under prefilming agent and normal operation respectively.
4. the method preparing composite corrosion inhibitor according to claim 3, is characterized in that, described solvent is deionized water or tap water.
5. the method preparing composite corrosion inhibitor according to claim 3, is characterized in that, the respective substance utilizing solvent directly to dissolve is as follows: described molybdate is potassium molybdate or magnesium molybdate; Described tungstate is potassium wolframate or ammonium tungstate; Described gluconate is Potassium Gluconate, calglucon or Menesia; Described rare-earth salts is zirconium nitrate, Yttrium trichloride, Yttrium trinitrate or acetic acid yttrium; Described zinc salt is Zinc Gluconate; Described stablizer is hexamethylenetetramine or Sodium dodecylbenzene sulfonate.
6. the using method of a composite corrosion inhibitor according to claim 1, it is characterized in that, in use, first i.e. step 1, the prefilming agent that pretreatment stage uses that is used for of preparation to be added in seawater or supplementary seawater and to make each component in final seawater reach the concentration requirement of prefilming agent respectively, then at normal temperatures rotating speed 80r/min ~ 120r/min or start recycle pump condition under, run at least 24h continuously, to form preservative protective film fast at steel surface; Step 2; proceed in normal inhibition seawater after pre-film; the inhibiter that the normal operating phase being about to preparation uses to be added in seawater or cooling system and to make each component final reach the concentration requirement of inhibiter under normal operation respectively, maintains inhibiter lower concentration and runs with the reparation realized protective membrane.
7. the using method of composite corrosion inhibitor according to claim 6, is characterized in that, in described step 1, normal temperature is 15 DEG C ~ 35 DEG C.
8. the using method of composite corrosion inhibitor according to claim 6, is characterized in that, in described step 1, normal temperature is 20 DEG C ~ 30 DEG C.
9. the using method of composite corrosion inhibitor according to claim 6, is characterized in that, in described step 1, continuous operating time is 24h ~ 48h.
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| US20140241939A1 (en) * | 2013-02-26 | 2014-08-28 | Baker Hughes Incorporated | Corrosion inhibitors for cooling water applications |
| CN108085665B (en) * | 2017-12-30 | 2020-02-07 | 仙桃市信达化工有限责任公司 | Novel industrial circulating cold water system prefilming agent and preparation method thereof |
| CN108425118B (en) * | 2018-03-21 | 2019-12-24 | 西安理工大学 | Quaternary compound vapor phase corrosion inhibitor for carbon steel and brass and preparation method thereof |
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| CN112226772B (en) * | 2019-07-15 | 2022-06-24 | 中国石油化工股份有限公司 | Composite corrosion inhibitor and method for inhibiting carbon steel corrosion in Fischer-Tropsch synthesis reaction water by using same |
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| CN111487376A (en) * | 2020-04-26 | 2020-08-04 | 西南石油大学 | Method for measuring interaction of components compounded by imidazoline derivative and corrosion inhibitor |
| EP3916127A1 (en) | 2020-05-26 | 2021-12-01 | AloxX GmbH | Composition and method for inhibition of corrosion of metals or metal alloys |
| CN111876784B (en) * | 2020-07-31 | 2022-02-22 | 西安热工研究院有限公司 | Corrosion inhibitor applied to SCAL type indirect cooling system and dosing method thereof |
| CN113981451A (en) * | 2021-08-13 | 2022-01-28 | 北京市古代建筑研究所 | Pre-filming corrosion inhibitor for iron cultural relics, and pre-filming and evaluation method thereof |
| CN114262070A (en) * | 2021-12-29 | 2022-04-01 | 贵州师范学院 | Phosphorus-free corrosion and scale inhibitor and preparation method and application thereof |
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