CN104843880A - Compound corrosion inhibitor and application of compound corrosion inhibitor in carbon steel material circulating cooling water system - Google Patents
Compound corrosion inhibitor and application of compound corrosion inhibitor in carbon steel material circulating cooling water system Download PDFInfo
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- CN104843880A CN104843880A CN201510241468.4A CN201510241468A CN104843880A CN 104843880 A CN104843880 A CN 104843880A CN 201510241468 A CN201510241468 A CN 201510241468A CN 104843880 A CN104843880 A CN 104843880A
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- corrosion inhibitor
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Abstract
The invention discloses a compound corrosion inhibitor and application of the compound corrosion inhibitor in a carbon steel material circulating cooling water system, and relates to the technical field of corrosion prevention in the cooling liquid used for all circulating cooling in smelting production. The compound corrosion inhibitor consists of polyepoxysuccinic acid, zinc vitriol, hydroxy ethidene diphosphonic acid and thiourea. The compound corrosion inhibitor is mixed into circulating cooling liquid to form a circulating cooling water system, and the circulating cooling is carried out with a carbon steel material. According to the compound corrosion inhibitor and the application thereof, the oneness of the collocation of whole organic phosphorus salt formula is avoided, and the collocation of surfactant thiourea and green and environment-friendly organic phosphorus salt is selected, so that synergistic effect among medicaments can be preferably played, the inhibition rate can reach above 90%, the biological degradability is good, the price is low and the materials are easy to obtain.
Description
Technical field
The present invention relates to the technical field of anticorrosion, particularly its compound of smelting and producing in all circulating cooling cooling fluids.
Background technology
Industrial circulating cooling water system solves the etching problem of system usually by adding medicament, due to the complicacy of industrial circulating cooling water system, the various etching problems of the obvious impossible resolution system simultaneously of single medicament, composite by several medicament, the mutual synergy between medicament can be given full play to, improve the over-all properties of medicament.But the most of compound drugs used at present, when draining into environment, are difficult to biological degradation, can cause environmental pollution, and inflammable and explosive.Therefore, a kind of circulating cooling liquid formula that is efficient, green, environmental protection is found particularly important.
40 ~ fifties of last century, the main corrosion using chromic salt and nitrite to suppress hardware of some countries of the U.S..Conventional chromic salt is its sodium salt, as Sodium chromate, potassiumchromate, sodium dichromate 99 and potassium bichromate.But because chromic salt has toxicity, easily cause the pollution of environment, thus its use receives strict restriction, and progressively replace by the medicament of poly-phosphate afterwards and organophosphorus system.As Sinopec Beijing swallow fossil oil stock company application number be 200410073666.6 patent documentation be exactly with polyaspartic acid material, 2-phosphate butane-1,2,4-tricarboxylic acid and this several organic phosphorus species of 2-di guanidine-acetic acid are main formula, although this formula inorganic salt formula comparatively before, phosphorus content declines to some extent, but in this formula, contained medicament only relates to organophosphorated salt system, too single, can not be applicable to complicated water-cycling-media.
Along with the day new development of nanotechnology, field of nanometer material technology is constantly being expanded to other field.When nano-fluid is as heat-eliminating medium, there is the heat dispersion that can improve oil engine, the effects such as the coefficient of heat transfer.But how making full use of the research that nano-fluid carries out the performances such as inhibition, dispersion and heat exchange becomes hot issue.
Because coastland Freshwater resources are relatively nervous, utilize seawater to be developed rapidly as industrial cooling water technology, be now widely used in the high water consumption Application Areass of industry cooling such as electric power, petrochemical industry, chemical industry.In seawater contained hardness and basicity relatively high, and operate under high concentration multiple for a long time, saltiness also can be higher.
When total hardness and total alkalinity sum be the high rigidity of 300 more than mg/L, the water quality of high alkalinity be applied in the but water cycle of carbon steel material time, then very easily corrosion is caused to carbon steel material.
Summary of the invention
The object of the present invention is to provide a kind of have good corrosion inhibition for the composite corrosion inhibitor in carbon steel material recirculating cooling water system.
The present invention forms primarily of poly-epoxy succinic acid, Zinc vitriol, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and thiocarbamide.
Thiocarbamide is a kind of adsorption corrosion inhibitor, has stronger polar group, in the solution with Cl
-generation competitive adsorption is reacted, and takes the lead in being adsorbed in steel surface, forms one deck hydrophobicity protective membrane, the destruction of chlorion is reduced, slowing down corrosion.
The present invention avoids the unicity of full stress-strain microcosmic salt system formula, chooses the collocation of tensio-active agent thiocarbamide and environmental type organophosphorated salt, more composite with zinc salt, the present invention can play the reciprocity between medicament better, improve inhibition efficiency, and biological degradability is good, cheap and be easy to get.
Another object of the present invention proposes with the application of composite corrosion inhibitor in carbon steel material recirculating cooling water system.
Composite corrosion inhibitor is mixed in circulating cooling liquid, forms recirculating cooling water system, carry out circulating cooling with carbon steel material.
Described circulating cooling liquid comprises basal liquid and with the Nano-meter SiO_2 after silane coupler modified
2.
Described poly-epoxy succinic acid accounts for 9 ~ 10% of recirculating cooling water system total mass, and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid accounts for 19 ~ 20% of recirculating cooling water system total mass, the Zn in Zinc vitriol
2+account for 0.15 ~ 0.2% of recirculating cooling water system total mass, thiocarbamide accounts for 9 ~ 10% of recirculating cooling water system total mass.
The Nano-meter SiO_2 of modification is doped with in the present invention
2, compare unmodified medicament, its specific surface area is less, and wetting ability reduces, and lipophilicity increases.And constitute New Cycle heat-eliminating medium with basal liquid, there is the function increasing formula heat dispersion, the coefficient of heat transfer etc.Thiocarbamide in formula inhibiter composition, is a kind of adsorptive type tensio-active agent, has stronger polar group, can in the solution with Cl
-generation competitive adsorption is reacted, and takes the lead in being adsorbed in steel surface, forms one deck hydrophobicity protective membrane, the destruction of chlorion is reduced, slowing down corrosion.The collocation of it and organophosphorated salt, opens up a kind of novel medicament collocation option.
The present invention avoids the unicity of full stress-strain microcosmic salt system formula collocation, choose the collocation of tensio-active agent thiocarbamide and environmental type organophosphorated salt, the present invention can play the synergy between medicament better, and corrosion inhibition rate can reach more than 90%, and biological degradability is good, cheap and be easy to get.
Innovative point of the present invention:
1, the corrosion inhibitor formula of research is usually mainly used in the water coolant medium of low alkalinity soft, the present invention is according to reality, choose liquid based on the materials such as calcium chloride, magnesium sulfate, sodium bicarbonate and sodium-chlor, simulation total hardness and total alkalinity sum are the high rigidity of 300 more than mg/L, the water-cycling-media of high alkalinity studies.
2, the present invention uses silane coupling agent to Nano-meter SiO_2
2carry out modification, and be doped in circulating cooling water medium, form novel nano fluid medium, change the physical and chemical performance of medicament, be improved the heat dispersion of cooling fluid, the effect of the coefficient of heat transfer etc.Make the present invention have more multifunctionality, more have practical value.
3, in the present invention's formula to comprise medicament be all environment-friendly and green type, choose organophosphorus system salt and tensio-active agent thiocarbamide is arranged in pairs or groups, change the character of microemulsion in solution, avoid the limitation that single medicament uses, utilize the synergy between dissimilar corrosion inhibitor, give full play to medicament usefulness, corrosion of carbon steel speed is declined.
Specific embodiments
The present invention simulates this kind of water-cycling-media, and total hardness and total alkalinity sum are high rigidity, the high alkalinity water quality of 300 more than mg/L, and the 1% modified Nano-meter SiO_2 that adulterates
2become circulating cooling medium of the present invention, with Q235B carbon steel for experiment material, composite with the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) of corrosion inhibition excellence based on poly-epoxy succinic acid (PESA) in formula, Zinc vitriol is selected to be zinc salt, to strengthen the synergy between medicament.In addition, the present invention also adds a kind of conventional collaborative medicament in research process, as chitosan, citric acid, sodium lauryl sulphate, water glass, thiocarbamide etc., by composite, compare, determine the combination of filling a prescription as Zinc vitriol, PESA, HEDP and thiocarbamide.Method of static coupon is utilized to carry out orthogonal experiment, determine that formulation content is 9 ~ 10 % that poly-epoxy succinic acid accounts for recirculating cooling water system total mass, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid accounts for 19 ~ 20 % of recirculating cooling water system total mass, Zinc vitriol accounts for 0.15 ~ 0.2 % of recirculating cooling water system total mass, and thiocarbamide accounts for 9 ~ 10 % of circulating cooling liquid total mass.Under this formula, corrosion inhibition rate can reach more than 90%.
Below in conjunction with concrete case study on implementation, the present invention will be described, but scope used in the present invention is not limited to the scope of case study on implementation.
Illustrate: and the medicine used in invention is commercially available prod or laboratory conventional medication.
Prepare water-cycling-media: Calcium Chloride Powder Anhydrous 0.555g, magnesium sulfate heptahydrate 0.4930g, sodium bicarbonate 0.6580g, the Nano-meter SiO_2 that sodium-chlor 0.168g, 1g are modified
2, add water and be made into 1000mL circulating cooling water medium.
The preparation of poly-epoxy succinic acid (PESA) solution: get the Epoxysuccinic acid 6g that solid content is 40%, distilled water is mixed with 1000mL.
The preparation of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) solution: get the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 6g that solid content is 50%, distilled water is mixed with 1000mL.
Zn
2+the preparation of solution: get Zinc vitriol 1.106g, distilled water is dissolved into 1000mL.
Experimental technique:
Corrosion inhibition is with reference to " National Standard of the People's Republic of China GB/T18175-2000, mensuration-the method for static coupon of water conditioner corrosion inhibition ", the method adopting lacing film to leave standstill, puts into the beaker of the water-cycling-media that 1000mL is housed, then drop into corresponding synergistic corrosion inhibitor in beaker by standard Q235B carbon steel test piece (long 50mm, wide 25mm, thick 2mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, tested after 3 days, weigh, calculate.
One, the screening of inhibiter composition:
Embodiment 1:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution.
Embodiment 2:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg chitosan.
Embodiment 3:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg Trisodium Citrate.
Embodiment 4:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg sodium lauryl sulphate.
Embodiment 5:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg water glass.
Embodiment 6:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg thiocarbamide.
Embodiment 7:
To each inhibiter composition added in the beaker of 1000mL circulating cooling medium is housed: 25mLPESA solution, 50mLHEDP solution, 15mLZn
2+solution, 150mg glucose.
The experimental result of above-described embodiment 1 ~ 7 is as following table:
Illustrate from table: in corrosion inhibitor formula, Zn
2+, the composite of PESA, HEDP and thiocarbamide be better than other formulas, its corrosion inhibition rate reaches 84.39%, and this compound scheme can select these medicine components to combine, and carries out compound screening further.
Two, the screening of inhibiter composition content:
Embodiment 8
The each component concentration composition of inhibiter in recirculating cooling water system: 1.2%PESA, 2.5%HEDP, 0.025%Zn
2+, 1.2% thiocarbamide.
Get 2mLPESA solution, 4.2mLHEDP solution, 1.2mLZn
2+solution, 12mg thiocarbamide, add circulating cooling medium, is made into 1000mL circulating cooling liquid.Put into wherein by standard Q235B carbon steel test piece (50 mm × 2, mm × 25 mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, test after 3 days, weigh, and calculate.
Embodiment 9
The each component concentration composition of inhibiter in recirculating cooling water system: 2.5%PESA, 5%HEDP, 0.05%Zn
2+, 2.5% thiocarbamide.
Get 4mLPESA solution, 8.3mLHEDP solution, 2mLZn
2+solution, 25mg thiocarbamide, add circulating cooling medium, is made into 1000mL circulating cooling liquid.Put into wherein by standard Q235B carbon steel test piece (50 mm × 2, mm × 25 mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, test after 3 days, weigh, and calculate.
Embodiment 10
The each component concentration composition of inhibiter in recirculating cooling water system: 5%PESA, 10%HEDP, 0.1%Zn
2+, 5% thiocarbamide.
Get 8mLPESA solution, 17mLHEDP solution, 5mLZn
2+solution, 50mg thiocarbamide, add circulating cooling medium, is made into 1000mL circulating cooling liquid.Put into wherein by standard Q235B carbon steel test piece (50 mm × 2, mm × 25 mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, test after 3 days, weigh, and calculate.
Embodiment 11
The each component concentration composition of inhibiter in recirculating cooling water system: 7.5%PESA, 15%HEDP, 0.15%Zn
2+, 7.5% thiocarbamide.
Get 12.5mLPESA solution, 25mLHEDP solution, 7.5mLZn
2+solution, 75mg thiocarbamide, add circulating cooling medium, is made into 1000mL circulating cooling liquid.Put into wherein by standard Q235B carbon steel test piece (50 mm × 2, mm × 25 mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, test after 3 days, weigh, and calculate.
Embodiment 12
The each component concentration composition of inhibiter in recirculating cooling water system: 9.9%PESA, 19.9%HEDP, 0.2%Zn
2+, 9.9% thiocarbamide.
Get 17mLPESA solution, 33mLHEDP solution, 10mLZn
2+solution, 100mg thiocarbamide, add circulating cooling medium, is made into 1000mL circulating cooling liquid.Put into wherein by standard Q235B carbon steel test piece (50 mm × 2, mm × 25 mm), during temperature 80 DEG C, not pre-film, every 4 hours supplementary first waters, test after 3 days, weigh, and calculate.
The experimental result of above-described embodiment 8 ~ 12 is as following table:
Embodiment 8 ~ 12 illustrates: Zn
2+, there is significant Synergistic inhibition between PESA, HEDP and thiocarbamide, when poly-epoxy succinic acid (PESA) accounts for 9 ~ 10% of recirculating cooling water system total mass, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) accounts for 19 ~ 20% of recirculating cooling water system total mass, and Zinc vitriol is (with Zn
2+meter) account for 0.15 ~ 0.2% of recirculating cooling water system total mass, when thiocarbamide accounts for 9 ~ 10% of recirculating cooling water system total mass, formula corrosion inhibition rate can reach more than 90%.This corrosion inhibitor formula is in the environment of heat-eliminating medium at dopen Nano fluid, has higher corrosion mitigating effect, and low-phosphorous, nontoxic, not containing flammable and explosive substance, be a kind of environment-friendly inhibiter.There is wide market application foreground.
Claims (5)
1. a composite corrosion inhibitor, is characterized in that forming primarily of poly-epoxy succinic acid, Zinc vitriol, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and thiocarbamide.
2. the application of composite corrosion inhibitor in carbon steel material recirculating cooling water system as claimed in claim 1, is characterized in that composite corrosion inhibitor to be mixed in circulating cooling liquid, forms recirculating cooling water system, carries out circulating cooling with carbon steel material.
3. the application of composite corrosion inhibitor in carbon steel material recirculating cooling water system according to claim 2, is characterized in that described circulating cooling liquid comprises basal liquid and with the Nano-meter SiO_2 after silane coupler modified
2.
4. the application of composite corrosion inhibitor in carbon steel material recirculating cooling water system according to Claims 2 or 3, it is characterized in that described poly-epoxy succinic acid accounts for 9 ~ 10% of recirculating cooling water system total mass, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid accounts for 19 ~ 20% of recirculating cooling water system total mass, the Zn in Zinc vitriol
2+account for 0.15 ~ 0.2% of recirculating cooling water system total mass, thiocarbamide accounts for 9 ~ 10% of recirculating cooling water system total mass.
5. the application of composite corrosion inhibitor in carbon steel material recirculating cooling water system according to claim 3, is characterized in that described basal liquid comprises calcium chloride, magnesium sulfate, sodium bicarbonate and sodium-chlor.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007016A (en) * | 2016-05-23 | 2016-10-12 | 南京工业大学 | Scale inhibiting-dispersing agent for three-time-concentrated low-temperature multiple-effect seawater desalination and preparation method thereof |
| CN111850568A (en) * | 2020-06-30 | 2020-10-30 | 中国石油天然气集团有限公司 | Corrosion inhibitor for preventing scale corrosion of oilfield ground gathering and transportation pipeline and preparation method thereof |
| CN113046753A (en) * | 2021-03-10 | 2021-06-29 | 武汉大学 | Compound corrosion inhibitor IM-SN-NaSiC and desalted water containing same |
| CN113149239A (en) * | 2021-04-06 | 2021-07-23 | 重庆电力高等专科学校 | Preparation of corrosion and scale inhibitor for circulating cooling water |
| CN113684483A (en) * | 2021-08-26 | 2021-11-23 | 常州市武进盛源化工有限公司 | Zinc chloride compound corrosion inhibitor for circulating cooling water and preparation method thereof |
| CN113755845A (en) * | 2021-09-06 | 2021-12-07 | 河北源清环保科技有限公司 | Corrosion inhibitor for circulating water system by using softened water as make-up water and preparation method thereof |
| CN113846329A (en) * | 2021-09-27 | 2021-12-28 | 上海趋寒流体科技有限公司 | Corrosion inhibitor composition for inhibiting corrosion of carbon steel in halide salt water |
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| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
| CN103030225A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Treatment process of circulating cooling water with leaked ammonia nitrogen |
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Patent Citations (2)
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| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
| CN103030225A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Treatment process of circulating cooling water with leaked ammonia nitrogen |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007016A (en) * | 2016-05-23 | 2016-10-12 | 南京工业大学 | Scale inhibiting-dispersing agent for three-time-concentrated low-temperature multiple-effect seawater desalination and preparation method thereof |
| CN111850568A (en) * | 2020-06-30 | 2020-10-30 | 中国石油天然气集团有限公司 | Corrosion inhibitor for preventing scale corrosion of oilfield ground gathering and transportation pipeline and preparation method thereof |
| CN113046753A (en) * | 2021-03-10 | 2021-06-29 | 武汉大学 | Compound corrosion inhibitor IM-SN-NaSiC and desalted water containing same |
| CN113149239A (en) * | 2021-04-06 | 2021-07-23 | 重庆电力高等专科学校 | Preparation of corrosion and scale inhibitor for circulating cooling water |
| CN113684483A (en) * | 2021-08-26 | 2021-11-23 | 常州市武进盛源化工有限公司 | Zinc chloride compound corrosion inhibitor for circulating cooling water and preparation method thereof |
| CN113755845A (en) * | 2021-09-06 | 2021-12-07 | 河北源清环保科技有限公司 | Corrosion inhibitor for circulating water system by using softened water as make-up water and preparation method thereof |
| CN113755845B (en) * | 2021-09-06 | 2023-07-25 | 河北源清环保科技有限公司 | Corrosion inhibitor for circulating water system with softened water as replenishing water and preparation method thereof |
| CN113846329A (en) * | 2021-09-27 | 2021-12-28 | 上海趋寒流体科技有限公司 | Corrosion inhibitor composition for inhibiting corrosion of carbon steel in halide salt water |
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Application publication date: 20150819 |