CN103820789A - Compounded carbon dioxide corrosion inhibitor - Google Patents
Compounded carbon dioxide corrosion inhibitor Download PDFInfo
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- CN103820789A CN103820789A CN201410061809.5A CN201410061809A CN103820789A CN 103820789 A CN103820789 A CN 103820789A CN 201410061809 A CN201410061809 A CN 201410061809A CN 103820789 A CN103820789 A CN 103820789A
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Abstract
A compounded carbon dioxide corrosion inhibitor belongs to a corrosion inhibitor anticorrosion technology. The invention relates to a corrosion inhibitor anticorrosion technology of carbon steel materials in CO2 environment, and especially relates to an efficient corrosion inhibitor obtained through the compounding and the corrosion inhibition cooperation of organic compounds comprising an imidazoline corrosion inhibitor and its derivative, alicyclic amine and its derivative, rosin amine and the like with thiourea and sodium dodecanesulphonate, so the corrosion of the carbon steel materials in the CO2 system can be effectively inhibited. The efficient corrosion inhibitor can be obtained through the compounding and the corrosion inhibition cooperation of the organic compounds with thiourea and sodium dodecanesulphonate. The compounded corrosion inhibitor is compact on the adsorption layer of the surface of carbon steel, so the corrosion inhibition effect of the corrosion inhibitor on the carbon steel materials in the CO2 corrosion system is improved, and the consumption of the corrosion inhibitor is effectively reduced. The compounded carbon dioxide corrosion inhibitor is of important guidance significance for developing efficient composite corrosion inhibitors. The compounded carbon dioxide corrosion inhibitor can be used for preventing CO2 corrosion in oil and gas fields.
Description
Technical field
The present invention relates to a kind of carbon steel material at CO
2anti-corrosion technology in environment, be particularly related to the inhibition synergistic effect of utilizing between the organic compound such as imidazolines inhibiter and derivative (wherein hydrophobic group carbon chain lengths C11-17), aliphatic amide and derivative (C12-18), rosin Amine D and thiocarbamide, sodium laurylsulfonate, by the composite high-efficient corrosion inhibitor that obtains, thereby effectively suppress CO
2the corrosion of corrosion system mild steel material.
Background technology
CO
2corrosion is the most general a kind of erosional forms running in production of hydrocarbons, and in the occasion that uses carbon steel and soft steel, it may cause higher erosion rate and serious local corrosion, in the recovery process of oil gas, owing to containing CO in oil and natural gas
2, down-hole string is caused to corrosion.CO
2corroding most typical feature is to present local spot corrosion, the corrosion of ringworm shape and mesa shaped pitting corrosion.Wherein, mesa shaped pitting corrosion is a kind of situation that corrosion process is the most serious, the percentage of perforation of this corrosion is very high. and erosion rate can reach 3mm/a～7mm/a conventionally, thereby drop to 6～18 months work-ing life that makes Oil/gas Well tubing string, cause huge financial loss to field produces, also cause certain environmental pollution simultaneously.
At present, suppress CO
2the technology of corrosion roughly has: adopt non-corrosive metal, the interior outside anticorrosive coating of equipment or pipeline, filling inhibiter etc.Practice shows, filling inhibiter is a kind of method with low cost, effective and easy to implement, is specially adapted to control the internal corrosion of Oil/gas Well tubing string and surface gathering and transferring pipeline.Contain nitrogen compound if tetrahydroglyoxaline is at CO
2under corrosive environment, there is good corrosion inhibition, and toxicity is little, is therefore widely applied.
The synergistic effect of inhibiter refers to a kind of performance adding and improved phenomenon due to other material (or inhibiter) of inhibiter.The raising of this corrosion mitigating effect, be not two components simply add and, but mutually promote, i.e. 1+1>2.Therefore utilize synergistic effect, can effectively improve the inhibition efficiency of inhibiter, reduce the usage quantity of inhibiter.
The inhibiter of practical application in industry, major part utilizes synergistic effect to form by many kinds of substance is composite.Such as the inhibiter of applying, be mostly composite and obtain by several materials in the inorganic acid systems such as hydrochloric acid, sulfuric acid, phosphoric acid.At CO
2in system, mainly utilized the inhibition synergistic effect between imidazolines inhibiter and thiocarbamide before.Except thiocarbamide, the invention still further relates to the inhibition synergism of sodium laurylsulfonate.
Summary of the invention
Technical problem to be solved by this invention is to provide the compounded combination of multiple inhibiter, utilize the inhibition synergistic effect between the organic compound such as imidazolines inhibiter and derivative thereof (wherein hydrophobic group carbon chain lengths C11-17), aliphatic amide and derivative (C12-18), rosin Amine D and thiocarbamide, sodium laurylsulfonate, by the composite high-efficient corrosion inhibitor that obtains.
The technical solution used in the present invention is that a kind of in the organic compound such as imidazolines inhibiter and derivative (wherein hydrophobic group carbon chain lengths C11-17), aliphatic amide and derivative (C12-18), rosin Amine D and thiocarbamide, sodium laurylsulfonate or two kinds are carried out composite.In compounded combination, the mass ratio of each material is: organic compound 10%～50%(optimum proportion 20%～30%), thiocarbamide 2%～10%(optimum proportion 3%～7%), sodium laurylsulfonate 5%～10%, surplus is water.Wherein organic compound is imidazolines inhibiter or derivatives thereof (wherein hydrophobic group carbon chain lengths C11-17), aliphatic amide or derivatives thereof (C12-18) or rosin Amine D.
Compositional type carbon dioxide corrosion inhibitor, is characterized in that: a kind of in organic compound and thiocarbamide, sodium laurylsulfonate or two kinds carry out composite, wherein, the mass ratio of each material is: organic compound 10%～50%, thiocarbamide 2%～10%, sodium laurylsulfonate 5%～10%, surplus is water; Wherein organic compound is imidazolines inhibiter or derivatives thereof, aliphatic amide or derivatives thereof or rosin Amine D.
Further, Compositional type carbon dioxide corrosion inhibitor, is characterized in that: organic compound 20%～30%, thiocarbamide 3%～7%, sodium laurylsulfonate 5%～10%;
Further, Compositional type carbon dioxide corrosion inhibitor, is characterized in that: the hydrophobic group carbon chain lengths of imidazolines inhibiter or derivatives thereof is C11-17.
Further, Compositional type carbon dioxide corrosion inhibitor, is characterized in that: the carbon chain lengths of aliphatic amide or derivatives thereof is C12-18.
Beneficial effect of the present invention is: utilize the inhibition synergistic effect between above-mentioned organic compound and thiocarbamide, sodium laurylsulfonate, by the composite high-efficient corrosion inhibitor that obtains.Compound corrosion inhibitor is finer and close at the adsorption layer of steel surface, thereby has improved inhibiter at CO
2corrosion inhibition to carbon steel material in corrosion system, and effectively reduced the consumption of inhibiter.Meanwhile, exploitation high efficiency composition inhibiter is had to important directive significance.The present invention can prevent CO for oil-gas field
2corrosion.
Accompanying drawing explanation:
Fig. 1 is that in the embodiment of the present invention 3, Q235 steel is adding the CO of different inhibiter
2the Nyquist collection of illustrative plates recording in saturated brine.
Embodiment:
embodiment 1:
Carry out compositely with inhibiter and other material according to the formula of table 1, listed percentage composition is mass percent, and surplus is distilled water.Wherein, take oleic acid and diethylenetriamine as raw material, through intermolecular amidation and intramolecular cyclization dehydration, can obtain inhibiter A.Concrete reaction equation is as follows:
Wang Xia, the prosperous Huaihe River of Shangguan, Hu Zhiqiang .2-aminoethyl 17 alkenyl imidazoline corrosion inhibitions are evaluated [J]. Speciality Petrochemicals, 2010,27 (1): 39.
R represents C
17h
33; Inhibiter A and Benzyl Chloride are carried out quaternary ammoniated, can obtain inhibiter B.Concrete reaction equation is as follows:
The combination of table 1 compound corrosion inhibitor
embodiment 2:
Corrosion experiment: experiment material therefor is Q235 steel, and its chemical composition (%, w) is C0.17, Si0.20, Mn0.45, P0.01, S0.03, Fe surplus.Test piece is of a size of 50mm × 10mm × 3mm.Adopt analytical reagent and 12 parts of NaCl solution that massfraction is 3.5% of distilled water preparation, the 1st part is blank solution, does not add any inhibiter; 2nd～5 parts are added respectively 50mg/L inhibiter A～D; Remain 7 parts and add respectively 50mg/L composite corrosion inhibitor a～g.
Test piece is first washed by rubbing with the hands with scrubbing powder, and with distilled water flushing, then clean through acetone, dehydrated alcohol, after hot blast drying, weigh, steel disc is hung on respectively in above-mentioned 12 parts of solution to logical 1h CO
2make solution saturated, experimental temperature is 60 ℃.Soak after 72h, test piece is taken out, put into aftertreatment fluid and soak 3min, then wash by rubbing with the hands with scrubbing powder, and with distilled water flushing, then clean through acetone, dehydrated alcohol, after hot blast drying, weigh, calculate erosion rate and corrosion inhibition rate by the weightlessness of test piece, experimental result is in table 2:
Table 2Q235 steel is at CO
2erosion rate in saturated brine and inhibiter corrosion inhibition rate
Result from table 2 can find out, under identical working concentration (50mg/L), one or both the composite uses in above-mentioned organic inhibitor and thiocarbamide, sodium laurylsulfonate, can effectively improve inhibition efficiency.
embodiment 3
Adopt analytical reagent and 12 parts of NaCl solution that massfraction is 3.5% of distilled water preparation, the 1st part is blank solution, does not add any inhibiter; 2nd～5 parts are added respectively 50mg/L inhibiter A～D; Remain 7 parts and add respectively 50mg/L composite corrosion inhibitor a～g.
Electrochemical impedance test: adopt traditional three-electrode system, working electrode material is Q235 steel, and supporting electrode is platinum plate electrode, and reference electrode is saturated calomel electrode (SCE).The disturbance current potential amplitude of electrochemical impedance spectroscopy is ± 5mV that, from high frequency toward low frequency sweep, range of scanned frequencies is 100kHz-0.01Hz.Electrochemical impedance test parameter is in table 3:
Table 3: the CO that adds different inhibiter
2the N recording in saturated brine
yquist collection of illustrative plates fitting parameter
Wherein R
ctwith R
ct0be respectively the charge transfer resistance adding when not adding inhibiter, inhibition efficiency (η) can calculate by following formula:
η=(R
ct-R
ct0)/R
ct （1）；
Result from table 3 can find out, under identical working concentration (50mg/L), by one or both and the composite use of above-mentioned organic inhibitor in thiocarbamide, sodium laurylsulfonate, can improve inhibition efficiency.Electrochemical impedance experiment proving again the corrosion inhibition of compound corrosion inhibitor be better than single inhibiter.
In sum, between the organic compound such as imidazolines inhibiter and derivative thereof (wherein hydrophobic group carbon chain lengths C11-17), aliphatic amide and derivative (C12-18), rosin Amine D and thiocarbamide, sodium laurylsulfonate, all there is inhibition synergistic effect, can obtain multiple compound corrosion inhibitor by a kind of in above-mentioned substance or two kinds after composite with organic compound, compound corrosion inhibitor is at CO
2in corrosion system, the corrosion mitigating effect of carbon steel is better than to single inhibiter, and has reduced inhibiter consumption.The present invention can prevent CO for oil-gas field
2corrosion, exploitation high efficiency composition inhibiter is had to important directive significance.
The above; it is only preferred embodiment of the present invention; it is not the restriction of the present invention being made to other form; any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations; but everyly do not depart from technical scheme content of the present invention; any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and remodeling, still belong to the protection domain of technical solution of the present invention.
Claims (4)
1. Compositional type carbon dioxide corrosion inhibitor, is characterized in that: a kind of in organic compound and thiocarbamide, sodium laurylsulfonate or two kinds carry out composite, wherein, the mass ratio of each material is: organic compound 10%～50%, thiocarbamide 2%～10%, sodium laurylsulfonate 5%～10%, surplus is water; Wherein organic compound is imidazolines inhibiter or derivatives thereof, aliphatic amide or derivatives thereof or rosin Amine D.
2. Compositional type carbon dioxide corrosion inhibitor as claimed in claim 1, is characterized in that: organic compound 20%～30%, thiocarbamide 3%～7%, sodium laurylsulfonate 5%～10%.
3. Compositional type carbon dioxide corrosion inhibitor as claimed in claim 1, is characterized in that: the hydrophobic group carbon chain lengths of imidazolines inhibiter or derivatives thereof is C11-17.
4. Compositional type carbon dioxide corrosion inhibitor as claimed in claim 1, is characterized in that: the carbon chain lengths of aliphatic amide or derivatives thereof is C12-18.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108865095A (en) * | 2018-09-17 | 2018-11-23 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of application of high-temperature corrosion inhibitor in tertiary oil recovery |
| CN110344064A (en) * | 2019-08-27 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of neutralization corrosion inhibiter |
| 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 |
| CN112341393A (en) * | 2020-11-10 | 2021-02-09 | 盘锦天诚源科技有限公司 | Metal corrosion inhibitor and preparation method thereof |
| CN112940700A (en) * | 2021-01-19 | 2021-06-11 | 中国石油天然气股份有限公司 | Nitrogen-containing corrosion inhibition main agent, gas-liquid two-phase corrosion inhibitor, and preparation method and application thereof |
| CN113005461A (en) * | 2019-12-20 | 2021-06-22 | 齐鲁工业大学 | Carbon steel descaling and cleaning corrosion inhibitor and cleaning agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865095A (en) * | 2018-09-17 | 2018-11-23 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of application of high-temperature corrosion inhibitor in tertiary oil recovery |
| CN110344064A (en) * | 2019-08-27 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of neutralization corrosion inhibiter |
| CN113005461A (en) * | 2019-12-20 | 2021-06-22 | 齐鲁工业大学 | Carbon steel descaling and cleaning corrosion inhibitor and cleaning agent |
| 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 |
| CN112341393A (en) * | 2020-11-10 | 2021-02-09 | 盘锦天诚源科技有限公司 | Metal corrosion inhibitor and preparation method thereof |
| CN112341393B (en) * | 2020-11-10 | 2023-09-22 | 盘锦天诚源科技有限公司 | Metal corrosion inhibitor and preparation method thereof |
| CN112940700A (en) * | 2021-01-19 | 2021-06-11 | 中国石油天然气股份有限公司 | Nitrogen-containing corrosion inhibition main agent, gas-liquid two-phase corrosion inhibitor, and preparation method and application thereof |
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| CN103820789B (en) | 2016-02-17 |
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