CN103436888A - High temperature copper corrosion inhibitor containing benzimidazole and preparation method of high temperature copper corrosion inhibitor - Google Patents
High temperature copper corrosion inhibitor containing benzimidazole and preparation method of high temperature copper corrosion inhibitor Download PDFInfo
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- CN103436888A CN103436888A CN2013103718781A CN201310371878A CN103436888A CN 103436888 A CN103436888 A CN 103436888A CN 2013103718781 A CN2013103718781 A CN 2013103718781A CN 201310371878 A CN201310371878 A CN 201310371878A CN 103436888 A CN103436888 A CN 103436888A
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Abstract
The invention discloses a high temperature copper corrosion inhibitor containing benzimidazole, and in particular relates to a copper corrosion inhibitor used in a high-temperature cycling cooling water system. The corrosion inhibitor comprises a mixture of benzimidazole (BI), benzotriazole (BTA), mercaptobenzothiazole (MBT), tolyltriazole (TTA), sodium hydroxide (NaOH) and water (H2O). Practice proves that dosage of the copper corrosion inhibitor can play an extremely good corrosion inhibiting effect on copper at a low temperature, and avoids the problem that a pure BTA type azole corrosion inhibitor is easily sublimated at a high temperature, so that the copper corrosion inhibitor is stilled excellent in corrosion and scale inhibition effect at a high temperature. The high temperature copper corrosion inhibitor containing benzimidazole is harmless to the environment, the corrosion rate to copper in a high temperature system is less than 0.001mm/a when the dosage of active components is 1-2mg/L, so that the copper corrosion inhibitor is an efficient environment-friendly high temperature copper corrosion inhibitor.
Description
Technical field
The present invention relates to industrial circulating cooling water and process, be specially adapted to a kind of benzoglyoxaline high temperature copper inhibitor and preparation method thereof that contains of copper material inhibition protection in Steel Plant's continuous cast mold water coolant, steam turbine of thermal power plant inner cold water.
Background technology
Along with the fast development of industrial economy, industrial water consumption sharply rises, and water coolant is the rich and influential family in process water, accounts for more than 80% of process water total amount.Therefore, how saving process water, accomplish that when using recirculated cooling water energy-saving consumption-reducing, water-saving and emission-reducing are protection of the environment, the basic demand that reduces costs, is also the primary goal that China realizes Sustainable development.
Continuous caster is the nucleus equipments of Steel Plant for continuous casting steel machine, and crystallizer is continuous caster " heart ", is the bottomless ingot mold for Forced water cooling.During work, the crystallizer inwall is bearing the static pressure of high-temperature molten steel and the mechanical stress produced with the frictional force of base shell relative movement etc. and the comprehensive action of thermal stresses, and its working conditions is very severe.In order to obtain qualified strand, crystallizer should meet that thermal conductivity is good, recrystallization temperature is high, thermal fatigue resistance, the primary conditions such as intensity is high, wear resistance good, long service life, therefore the only selection that the copper material that meets above-mentioned condition is crystallization continuous casting device, the inhibition of copper material has also become to prevent bleed-out, guarantees the important process link of the normal stably condensation shaping ejection of steel.Equally, in the process of generator generating, stator and rotor can produce a large amount of heats, must through the hollow copper conductor, constantly take away heat with heat-eliminating medium, reduce as much as possible the temperature of generator key position, once copper conductor is corroded, just likely cause the Serious Accidents such as burn-down of electric motor blast, loss is greatly.Visible, the inhibition problem that solves copper material under the high temperature system has become the task of top priority in recirculated cooling water field.
In recent years, take the azole compounds that benzotriazole is representative is often used as the copper inhibitor in industrial circulating cooling water.Chinese patent: (CN101974760A) disclose a kind of oxidization-resistant copper corrosion inhibitor for recirculating cooling water system; this inhibiter effective constituent is by a kind of or compositions of mixtures of benzotriazole, methyl benzotriazazole and mercaptobenzothiazole; reduce the decomposition of chlorine residue to organophosphate and polymer antisludging agent when can be protected the copper product in the recirculating cooling water system that uses chloride sterilant; improve the sterilizing ability of circulating water system, thereby reduce the processing costs of circular water treating system and improve treatment effect.Chinese patent: the preparation and the surface treatment method that (CN102206826A) disclose the multiple matching type copper inhibitor mainly formed by benzotriazole, 2-mercaptobenzothiazole.Described inhibiter is due to benzotriazole, methyl benzotriazazole and the mercaptobenzothiazole film forming speed is fast, corrosion mitigating effect good, can effectively avoid the generation of the corrosion products such as copper material surface ventilation breather under higher concentration.But their sublimation temperature is lower (as the sublimation temperature of BTA is 95 ℃) all, easy desorption when the wall temperature of interchanger is higher and reduce corrosion mitigating effect therefore only uses the azole compounds of above-mentioned routine unsatisfactory as the corrosion mitigating effect of copper inhibitor in high-temperature systems.In this case, be badly in need of the copper inhibitor that a kind of chemical stability is good, high temperature resistant, certain threshold effect is arranged and have good synergistic effect with other medicament.
Summary of the invention
The object of the present invention is to provide a kind of industrial circulating cooling water that is applicable to, especially under the high temperature system containing benzoglyoxaline high temperature copper inhibitor and application thereof.This kind of copper inhibitor has the corrosion inhibiting ability of good thermostability, excellence, and cost is lower, environmentally friendly.
The technical solution that realizes the object of the invention is:
A kind of containing benzoglyoxaline high temperature copper inhibitor, described inhibiter is by benzimidazoles compound (BI), benzotriazole (BTA), mercaptobenzothiazole (MBT), methyl benzotriazazole (TTA), sodium hydroxide (NaOH) and water (H
2o) form, each constituent mass mark is: benzimidazoles compound 2% ~ 3%, benzotriazole 1% ~ 1.5%, mercaptobenzothiazole 0.5% ~ 0.7%, methyl benzotriazazole 0.5% ~ 0.7%, sodium hydroxide 1% ~ 2%, surplus are deionized water.
Wherein, benzimidazoles compound is selected one or more the mixture in 1-tolimidazole, 2-tolimidazole and 2-Phenylbenzimidazole.The preferred 2-Phenylbenzimidazole of benzoglyoxaline.
The above-mentioned preparation method containing benzoglyoxaline high temperature copper inhibitor, comprise the following steps: first sodium hydroxide is added to the water, again above-mentioned azole compounds (benzimidazoles compound (BI), benzotriazole (BTA), mercaptobenzothiazole (MBT), methyl benzotriazazole (TTA)) is at room temperature slowly stirred and adds wherein in proportion, continue to stir 1 ~ 2 hour, obtain containing benzoglyoxaline high temperature copper inhibitor when solution is clarified without insoluble impurities;
Each constituent mass mark is: benzimidazoles compound 2% ~ 3%, benzotriazole 1% ~ 1.5%, mercaptobenzothiazole 0.5% ~ 0.7%, methyl benzotriazazole 0.5% ~ 0.7%, sodium hydroxide 1% ~ 2%, surplus are deionized water.
In the system of its sublimation temperature below 95 ℃, film forming speed is fast, corrosion mitigating effect good for BTA, but in the system of comparatively high temps easy desorption and reduce corrosion mitigating effect; Although MBT and TTA film forming speed are slightly slow, sublimation temperature is higher, is difficult for desorption after film forming; Main component BI has fabulous thermostability, even also can good protection effect be arranged to copper product under the high temperature system of 350 ℃.
The present invention compared with prior art, its remarkable advantage is: (1) is of the present invention containing benzoglyoxaline high temperature copper inhibitor, at high temperature the corrosion mitigating effect of copper material is better than to common azole copper inhibitor, even under the high temperature system of 350 ℃, still can reaches more than 99% to the corrosion inhibition rate of copper; (2) of the present invention containing benzoglyoxaline high temperature copper inhibitor, because raw material sources are extensive, preparation technology is simple, and cost is low, does not increase the user equipment investment.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The accompanying drawing explanation
In Fig. 1 embodiment of the present invention 6, system adds the corrosion rate (black) of formula before 8 to I type red copper standard corrosion coupon and the corrosion rate (white) after dosing varies with temperature diagram under high temperature (150 ± 5 ~ 350 ± 5 ℃).
In Fig. 2 embodiment of the present invention 7, system adds respectively corrosion rate (black) and the corrosion rate (white) dosing after of formula before 8 to I type red copper, brass, copper-nickel alloy standard corrosion coupon and illustrates under 350 ± 5 ℃.
Embodiment
below in conjunction with specific embodiment, composition and the effect containing benzoglyoxaline high temperature copper inhibitor of the present invention is described further.
Preparation method containing benzoglyoxaline high temperature copper inhibitor, comprise the following steps: first sodium hydroxide is added to the water, again benzimidazoles compound (BI), benzotriazole (BTA), mercaptobenzothiazole (MBT), methyl benzotriazazole (TTA) are at room temperature slowly stirred and add wherein in proportion, continue to stir 1 ~ 2 hour, obtain containing benzoglyoxaline high temperature copper inhibitor when solution is clarified without insoluble impurities.
The inhibiter that uses forms as shown in table 1, and the experiment of using moisturizing water-quality guideline used is as shown in table 2.
Composition containing benzoglyoxaline high temperature copper inhibitor used in table 1 embodiment
| Formula | BI | BTA | MBT | TTA | NaOH | H 20 |
| 1 | 2.0% | 1.0% | 0.5% | 0.5% | 1.0% | 95.0% |
| 2 | 2.5% | 1.0% | 0.5% | 0.5% | 1.0% | 94.5% |
| 3 | 2.0% | 1.5% | 0.5% | 0.5% | 1.0% | 94.5% |
| 4 | 2.5% | 1.5% | 0.5% | 0.5% | 1.0% | 94.0% |
| 5 | 3.0% | 1.0% | 0.6% | 0.6% | 1.0% | 93.8% |
| 6 | 3.0% | 1.0% | 0.7% | 0.7% | 1.0% | 93.6% |
| 7 | 3.0% | 1.5% | 0.6% | 0.6% | 1.0% | 93.3% |
| 8 | 3.0% | 1.5% | 0.7% | 0.7% | 1.0% | 93.1% |
The moisturizing water quality that table 2 experiment is used
| The water sample source | Three 2# of the steel mill continuous casting system moisturizings of Ma Gang company |
| pH | 7.5 |
| Calcium ion/(with CaCO 3Meter mg/L) | <5mg/L |
| Cl -/ (mg/L) | 10mg/L |
| Total alkalinity/(mmol/L) | 1.2 |
| Total hardness/(mmol/L) | 0.5 |
| Specific conductivity/(μ scm -1) | 205 |
By specification, be 50mm * 25mm * 2mm, surface-area is 28cm
2i type brass, red copper or copper-nickel alloy standard corrosion coupon hang on the titanium steel autoclave kettle cover below that useful volume is about 500mL, fill with the moisturizing shown in table 2 in still, guarantee that kettle cover covers tightly the rear water surface and can not have the copper test piece.Add the composite corrosion inhibitor in table 1, in the warranty test water sample, the effective content of azole compounds is 2mg/L, after sealing, is placed in the constant temperature oven of assigned temperature, takes out to roll every 1 hour and stirs 1min, after 72h, takes out and is cooled to room temperature.Moisturizing in still is taken out, calculate the copper ion concentration in moisturizing after processing by standard method and obtain in the namely copper test piece of cupric ion total amount in moisturizing with this quality partly that is corroded.Carry out blank test by same method, in conjunction with both test-results, calculate corrosion inhibition rate.
embodiment 1choose formula 1, test the corrosion mitigating effect of its (150 ± 5 ℃, 200 ± 5 ℃, 250 ± 5 ℃, 300 ± 5 ℃, 350 ± 5 ℃) I type red copper standard corrosion coupon at high temperature, result is as shown in the table:
| Temperature (℃) | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| 150±5℃ | 0.0228 | 0.0016 |
| 200±5℃ | 0.0255 | 0.0019 |
| 250±5℃ | 0.0287 | 0.0020 |
| 300±5℃ | 0.0301 | 0.0024 |
| 350±5℃ | 0.0320 | 0.0027 |
embodiment 2choose formula 1, test it to the corrosion mitigating effect at 350 ± 5 ℃ of lower I type red coppers, brass, copper-nickel alloy standard corrosion coupon, result is as shown in the table:
| Copper material | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| Red copper | 0.0320 | 0.0027 |
| Brass | 0.0329 | 0.0023 |
| Copper-nickel alloy | 0.0331 | 0.0029 |
embodiment 3choose formula 4, test the corrosion mitigating effect of its (150 ± 5 ℃, 200 ± 5 ℃, 250 ± 5 ℃, 300 ± 5 ℃, 350 ± 5 ℃) I type red copper standard corrosion coupon at high temperature, result is as shown in the table:
| Temperature (℃) | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| 150±5℃ | 0.0228 | 0.0015 |
| 200±5℃ | 0.0255 | 0.0017 |
| 250±5℃ | 0.0287 | 0.0018 |
| 300±5℃ | 0.0301 | 0.0021 |
| 350±5℃ | 0.0320 | 0.0026 |
| Temperature (℃) | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| 150±5℃ | 0.0228 | 0.0014 |
| 200±5℃ | 0.0255 | 0.0016 |
| 250±5℃ | 0.0287 | 0.0018 |
| 300±5℃ | 0.0301 | 0.0021 |
| 350±5℃ | 0.0320 | 0.0025 |
| Copper material | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| Red copper | 0.0320 | 0.0025 |
| Brass | 0.0329 | 0.0022 |
| Copper-nickel alloy | 0.0331 | 0.0027 |
embodiment 6choose formula 8, test the corrosion mitigating effect of its (150 ± 5 ℃, 200 ± 5 ℃, 250 ± 5 ℃, 300 ± 5 ℃, 350 ± 5 ℃) I type red copper standard corrosion coupon at high temperature, result is as shown in the table:
| Temperature (℃) | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| 150±5℃ | 0.0228 | 0.0014 |
| 200±5℃ | 0.0255 | 0.0015 |
| 250±5℃ | 0.0287 | 0.0017 |
| 300±5℃ | 0.0301 | 0.0019 |
| 350±5℃ | 0.0320 | 0.0022 |
As shown in Figure 1, along with system temperature is increased to 350 ± 5 ℃, the corrosion mitigating effect of medicament slightly reduces, but fill a prescription, 8 still can keep that copper material is had to good corrosion mitigating effect.
embodiment 7choose formula 8, test it to the corrosion mitigating effect at 350 ± 5 ℃ of lower I type red coppers, brass, copper-nickel alloy standard corrosion coupon, result is as shown in the table:
| Copper material | Blank corrosion rate (mm/a) | Dosing post-etching rate (mm/a) |
| Red copper | 0.0320 | 0.0022 |
| Brass | 0.0329 | 0.0019 |
| Copper-nickel alloy | 0.0331 | 0.0024 |
As shown in Figure 2, for different copper materials, 8 the corrosion mitigating effect of filling a prescription can be slightly different, comprehensively it seems, formula of the present invention is best to the corrosion mitigating effect of brass, slightly is better than red copper and copper-nickel alloy.
embodiment 8above-mentioned formula 8 is applied to three steel mills 2 of Ma'anshan Iron and Steel Corp
#continuous casting system, moisturizing water quality is as table 2, and recirculated water concentration rate 1.2 ~ 1.5, compare as table 3 with other scheme treatment effect.
Three steel mills 2 of table 3 Ma Gang company
#treatment effect synopsis when continuous casting system recirculated water adds different inhibiter
| No | Time | The inhibiter main component | The inhibiter cost | The crystallizer life-span |
| 1 | 2007.02~2010.08 | BTA+TTA+MBT | ~ 3 ten thousand yuan/month | 50 ~ 200 stoves |
| 2 | 2010.09~2010.12 | NaMoO 4+BTA | ~ 30 ten thousand yuan/month | 50 ~ 250 stoves |
| 3 | 2011.01~2013.06 | BI+BTA+MBT+TTA | ~ 5 ten thousand yuan/month | 300 ~ 600 stoves |
Result shows, benzoglyoxaline type high temp copper inhibitor of the present invention is no more than 0.0027mm/a to the corrosion rate of copper material under 350 ± 5 ℃ of systems, and corrosion inhibition rate all can reach more than 99.73%.
Claims (4)
1. one kind contains benzoglyoxaline high temperature copper inhibitor, it is characterized in that: described inhibiter is comprised of benzimidazoles compound, benzotriazole, mercaptobenzothiazole, methyl benzotriazazole, sodium hydroxide and water, and each constituent mass mark is: benzimidazoles compound 2% ~ 3%, benzotriazole 1% ~ 1.5%, mercaptobenzothiazole 0.5% ~ 0.7%, methyl benzotriazazole 0.5% ~ 0.7%, sodium hydroxide 1% ~ 2%, surplus are deionized water.
2. according to claim 1 containing benzoglyoxaline high temperature copper inhibitor, it is characterized in that: benzimidazoles compound is selected one or more the mixture in 1-tolimidazole, 2-tolimidazole and 2-Phenylbenzimidazole.
3. according to claim 2 containing benzoglyoxaline high temperature copper inhibitor, it is characterized in that: the preferred 2-Phenylbenzimidazole of benzoglyoxaline.
4. one kind prepares arbitrary described method containing benzoglyoxaline high temperature copper inhibitor in claim 1-3, it is characterized in that comprising the following steps: first sodium hydroxide is added to the water, again the azole compounds described in claim 1 or 2 or 3 is at room temperature slowly stirred and adds wherein in proportion, continue stirring and within 1 ~ 2 hour, obtain containing benzoglyoxaline high temperature copper inhibitor;
Each constituent mass mark is: benzimidazoles compound 2% ~ 3%, benzotriazole 1% ~ 1.5%, mercaptobenzothiazole 0.5% ~ 0.7%, methyl benzotriazazole 0.5% ~ 0.7%, sodium hydroxide 1% ~ 2%, surplus are deionized water.
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| US10190222B2 (en) | 2015-05-28 | 2019-01-29 | Ecolab Usa Inc. | Corrosion inhibitors |
| US10519116B2 (en) | 2015-05-28 | 2019-12-31 | Ecolab Usa Inc. | Water-soluble pyrazole derivatives as corrosion inhibitors |
| US10669637B2 (en) | 2015-05-28 | 2020-06-02 | Ecolab Usa Inc. | Purine-based corrosion inhibitors |
| CN111954729A (en) * | 2018-01-03 | 2020-11-17 | 埃科莱布美国股份有限公司 | Process and method for reducing corrosion of metals in water |
| US10858585B2 (en) | 2018-01-03 | 2020-12-08 | Ecolab Usa Inc. | Benzotriazole derivatives as corrosion inhibitors |
| JP2021091974A (en) * | 2015-05-28 | 2021-06-17 | エコラボ ユーエスエー インコーポレイティド | 2-Substituted imidazole and benzimidazole corrosion inhibitors |
| CN115491679A (en) * | 2022-10-15 | 2022-12-20 | 厦门竞高电镀有限公司 | Environment-friendly copper anti-blushing agent and preparation thereof |
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| CN115491679A (en) * | 2022-10-15 | 2022-12-20 | 厦门竞高电镀有限公司 | Environment-friendly copper anti-blushing agent and preparation thereof |
| CN115491679B (en) * | 2022-10-15 | 2024-04-02 | 厦门竞高电镀有限公司 | Environment-friendly copper anti-discoloration agent and preparation thereof |
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