CN102344789A - Hydrogen sulfide resistant corrosion inhibitor for oil and gas well pipeline - Google Patents
Hydrogen sulfide resistant corrosion inhibitor for oil and gas well pipeline Download PDFInfo
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- CN102344789A CN102344789A CN2010105829855A CN201010582985A CN102344789A CN 102344789 A CN102344789 A CN 102344789A CN 2010105829855 A CN2010105829855 A CN 2010105829855A CN 201010582985 A CN201010582985 A CN 201010582985A CN 102344789 A CN102344789 A CN 102344789A
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Abstract
The invention provides a hydrogen sulfide resistant corrosion inhibitor for an oil and gas well pipeline. The hydrogen sulfide resistant corrosion inhibitor comprises, by weight, 40-60 parts of modified imidazoline, 3-7 parts of acrylic acid-hydroxypropyl acrylate, 3-7 parts of hydrolyzed polymaleic anhydride and 35-45 parts of composite sensitizing emulsifier. The preparation of modified imidazoline comprises steps of: adding 676kg of lauric acid and 260kg of diethylenetriamine into a reaction kettle; stirring and raising a temperature to 140 DEG C; slowly raising the temperature to 230 DEG C; keeping a degree of vacuum at -0.018MPA; reacting for 4 h; cooling to lower than 70 DEG C; and discharging to obtain an intermediate. The modification of the intermediate comprises steps of: adding 100kg of ethanol and 385kg of intermediate into the reaction kettle and stirring to heat to 40 DEG C; adding 235kg of carbon disulfide into 280kg of ethanol; mixing and dropping to the reaction kettle slowly with a dropping time of 2 h at 50 DEG C; reacting for 15 h; emptying and cooling to obtain a product. Triethanolamine and polyoxyethylene nonyl phenol ether are mixed; acrylic acid-hydroxypropyl acrylate and hydrolyzed polymaleic anhydride are mixed; and the above materials are placed in the reaction kettle, added with water and mixed at 20-35 DEG C for 50-70 min until formation of dope to obtain the corrosion inhibitor.
Description
Technical field
The present invention relates to the screening and the preparation of technology, especially inhibiter of the anti-hydrogen sulfide inhibition of oil gas well conduit and equipment, this product has special effect to the corrosion that suppresses pipeline and equipment hydrogen sulfide.
Background technology
Oil gas well mining, the protection against corrosion of its pipe-line equipment are serious problems, and the Sweet natural gas major part contains H
2S and CO
2, make pipe interior contact H
2S and CO
2, it is conspicuous producing corrosion.Fe+H for example
2S → FeS+2H; CO
2+ H
2O+Fe → FeCO
3+ H
2Chemical reaction, the hydrogen that cathodic reaction is separated out advances in people's steel, the formed hydrogen pressure of gaseous hydrogen causes material fragility cracking, finally causes the corrosion of spool.The special corrosion-resistant material of exploitation like the SM-S and the SM-SS steel of Sumitomo Metal Industries, can effectively prevent the H 2 S stress corrosion cracking, but can not prevent H at present
2S and CO
2General corrosion, this corrosion-resistant material cost height is not had an optimistic view of by market simultaneously.Therefore, must adopt its more reasonably guard technology measure, in the work-ing life of improving oil field equipment, adopt improved inhibiter to be undoubtedly the optimal selection of preservative oil gas field equipment.
Retrieving information discloses: 1. people such as Dong Ze China utilize computer-controlled electrokinetic potential scanning method studied the oil soluble imidazolines to carbon steel at slightly acidic H
2Corrosion inhibition in the S aqueous solution; 2. people such as sieve Zhe beautiful woman has studied through the naphthenic acid imidazoline inhibiter HM that obtains through ethoxylation and quaterisation modification, HMO at H
2Good corrosion inhibition is arranged in the S medium; 3. people such as king's mountain valley with clumps of trees and bamboo brightness has studied " a kind of imidazolines inhibiter that can be used for the wet hydrogen sulfide protection of oil refining apparatus "; Above-mentioned data is all estimated its corrosion mitigating effect, but has significantly different with research object of the present invention.
The present invention is intended to overcome the problem in the existing production technology, and the etching reagent of the anti-H 2 S that provides had both been protected oil gas well conduit and equipment, had reduced the manufacturing cost of former inhibiter again, had important use value.
Summary of the invention
The objective of the invention is: be provided for the inhibiter of oil gas well, synergy on the basis of modification produces strong synergetic property, has reached original design requirement.
The objective of the invention is to realize like this: a kind of corrosion inhibiter that is used for the anti-hydrogen sulfide of oil gas well conduit and equipment; Raw material is prepared with parts by weight, is made up of modified imidazoline 40-60 part, acrylic acid-hydroxypropyl acrylate 3-7 part, hydrolyzed polymaleic anhydride 3-7 part, composite sensitization emulsifying agent 35-45 part; Through preparing:
The preparation of a, modified imidazoline: add lauric acid 676kg, diethylenetriamine 260kg to reaction kettle, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes; Kept 2.5 hours down at 150 ℃, be warming up to 190 ℃, kept 30 minutes, vacuum tightness is-0.015MPA; Slowly be warming up to 230 ℃ then, vacuum tightness remained on-0.018MPA, reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
With the intermediate modification: to reaction kettle add ethanol 100kg, intermediate 385kg stirs, and is warming up to 40 ℃; 235kg dithiocarbonic anhydride is joined in the ethanol of 280kg, slowly be added drop-wise to after mixing in the reaction kettle, 2 hours dropping time, 50 ℃ of controlled temperature, balanced reaction 15 hours, emptying are lowered the temperature to such an extent that modified imidazoline is subsequent use;
B, composite sensitization emulsifying agent composite: trolamine and polyoxyethylene nonylphenol ether is subsequent use by weight the mixed back that stirs of 1:1;
C, before using vinylformic acid-Propylene glycol monoacrylate, mix itself and hydrolyzed polymaleic anhydride subsequent use earlier;
Preparation: place reaction kettle to add the water stirring material of a, b, c, controlled temperature is 20-35 ℃, and the time is 50-70 minute, forms thick thing and promptly gets inhibiter.
Described inhibiter, the color of the intermediate of modified imidazoline are black, and nonirritant ammonia flavor does not dissolve in normal-temperature water, and acid number is less than 0.5mgKOH/g.
Described inhibiter, product is 20-100mg/L to the dosage of the anti-hydrogen sulfide inhibition of pipeline and equipment.
Described inhibiter, the batching of selecting raw material and synthesis modification tetrahydroglyoxaline for use is the commercially available prod.
Product of the present invention is to imidazoline modified action principle: inhibition is adsorption; Especially for positively charged ion and amphoterics; Effect through polar group on its molecule; Make it be adsorbed on the metallic surface; Change the charge distribution and the interfacial property of metallic surface so on the one hand; Make the tending towards stability of energy state of metallic surface, thereby increase the activation energy of corrosion reaction, corrosion speed is slowed down; Non-polar group on the inhibiter that is adsorbed on the other hand still can form one deck hydrophobicity protective membrane in the metallic surface, hampers the transfer of electric charge or the material relevant with corrosion reaction, thereby inhibition speed is reduced.Use the easy and tetrahydroglyoxaline intermediate reaction of dithiocarbonic anhydride, generate the thioureido tetrahydroglyoxaline, be modified imidazoline.Thiocarbamide is mainly used in metal pickling corrosion inhibitor, and in particular solution, the sulphur arteries and veins can produce absorption behavior in the metallic surface, and this its produces the major reason of corrosion inhibition just.
Product of the present invention is to sensitization emulsifying agent compound action principle: emulsifying agent shared content in composite corrosion inhibitor exceeds several times than its content shared in common oil in water emulsion; Make that emulsive liquid phase dielectric hydrophobic substance still can keep stable relatively under the very low situation of the concentration of inhibiter in water body, exist with the high dispersing state; Tensio-active agent in the composite sensitization emulsifying agent is subjected to the effect of hydrated metal ion easily at metal interface; Its oleophylic hydrophilic balance shifts; By wetting ability to the lipophilicity transition; Bring out the liquid dielectric hydrophobic substance of emulsification dispersive unstability; Promote medicament to separate out, be adsorbed on automatically the metallic surface and form the hydrophobic liquid film of high resistant, the performance corrosion inhibition in the preferential unstability of metal interface.
The corrosion inhibiter that the present invention obtains; Special feature is that it does not belong to solution-type; It contains liquid dielectric hydrophobic substance and special composite sensitization emulsifying agent; Make it with after very low dosage adds in the water body; The liquid dielectric hydrophobic substance that carries the modified imidazoline corrosion inhibiter is present in the water body with the metastable condition of high degree of dispersion; And can with preferentially separate out after the metal surface contacts in this solid liquid interface (or giving hot interface) unstability; Automatically be adsorbed on the metal surface and form the high resistant hydrophobic membrane; Make corrosion inhibiter reach very high numerical value at the local concentration of solid liquid interface; Make drug effect be able to ultra performance; And then save medication to greatest extent; Add the effect of modified imidazoline agent in this liquid film; Just can suppress the generation of the corrosion of metal most effectively, show technological progress.
Embodiment
Embodiment 1
Raw material is prepared with parts by weight, is made up of for 40 parts 50 parts of modified imidazolines, 5 parts of acrylic acid-hydroxypropyl acrylates, 5 parts of hydrolyzed polymaleic anhydrides, 40 parts of composite sensitization emulsifying agents, water; Through preparing:
A, modified imidazoline preparation: add lauric acid 676kg, diethylenetriamine 260kg to reaction kettle, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes; Kept 2.5 hours down at 150 ℃; Be warming up to 190 ℃, kept 30 minutes, make vacuum tightness be-0.015MPA; Slowly be warming up to 230 ℃ then, vacuum tightness remained on-0.018MPA, reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
Intermediate modification with the last step: add ethanol 100kg, intermediate 385kg stirring to reaction kettle, be warming up to 40 ℃; 235kg dithiocarbonic anhydride is joined in the ethanol of 280kg, be mixed into solution, slowly be added drop-wise in the reaction kettle, the dropping time is 2 hours, and temperature is controlled at 50 ℃; Balanced reaction 15 hours, emptying lower the temperature modified imidazoline;
B, the preparation of composite sensitization emulsifying agent: trolamine and polyoxyethylene nonylphenol ether are promptly got by weight mixed the stirring of 1:1;
C, first vinylformic acid-Propylene glycol monoacrylate is added in the hydrolyzed polymaleic anhydride add after the mixing again;
Total preparation: place reaction kettle to add the water stirring material of a, b, c, controlled temperature is 35 ℃, and the time is 60 minutes, forms thick thing and promptly gets inhibiter.
Embodiment 2
Get 55 parts of modified imidazolines, 3 parts of vinylformic acid-Propylene glycol monoacrylates, 7 parts of hydrolyzed polymaleic anhydrides, 35 parts of composite sensitization emulsifying agents with parts by weight; Add reaction kettle after disposing respectively; Stir; Time is 60 minutes; Controlled temperature is 30 ℃; Form thick thing and get product, the step of its a, b, c is with embodiment 1.
Embodiment 3
Get 45 parts of modified imidazolines with parts by weight; 7 parts of vinylformic acid-Propylene glycol monoacrylates; 3 parts of hydrolyzed polymaleic anhydrides; 45 parts of composite sensitization emulsifying agents add reaction kettle after disposing respectively, add 30 parts of stirrings of water; Time is 50 minutes; Controlled temperature is 25 ℃, forms thick thing and gets product, and the step of its a, b, c is with embodiment 1.
The present invention is through following its performance of products of test data checking.
Material: A3 steel, two-electrode system
Fluid: 90% salt solution (3% NaCl), 10% kerosene, logical CO
2To saturated, logical H
2S to 200mg/L.
Condition: 50 ℃, adopt petroleum industry standard SY/T5273-2000 to carry out the corrosion inhibition test, move 168 hours, experimental result is seen table.
Learn by last table, add inhibiter after, corrosion mitigating effect is obvious, has effectively controlled the uniform corrosion of oil gas well oil-water mixture and at CO
2-H
2Point corrosion in the S system is controlled in the regulation 0.076mm/a scope of petroleum industry.
The testing ground checking:
Embodiment 1 inhibiter is used for H
2S content is 147mg/L, and salinity is the oil country tubular good of 120000 mg/L, and dosage is 60mg/L; In pipeline, hang the A3 steel disc for the monitoring lacing film, take out steel disc after three months, erosion rate is 0.01517mm/a.
Claims (4)
1. corrosion inhibiter that is used for the anti-hydrogen sulfide of oil gas well conduit and equipment; It is characterized in that: raw material is prepared with parts by weight, is made up of modified imidazoline 40-60 part, acrylic acid-hydroxypropyl acrylate 3-7 part, hydrolyzed polymaleic anhydride 3-7 part, composite sensitization emulsifying agent 35-45 part; Through preparing:
The preparation of a, modified imidazoline: add lauric acid 676kg, diethylenetriamine 260kg to reaction kettle, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes; Kept 2.5 hours down at 150 ℃, be warming up to 190 ℃, kept 30 minutes, vacuum tightness is-0.015MPA; Slowly be warming up to 230 ℃ then, vacuum tightness remained on-0.018MPA, reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
With the intermediate modification: to reaction kettle add ethanol 100kg, intermediate 385kg stirs, and is warming up to 40 ℃; 235kg dithiocarbonic anhydride is joined in the ethanol of 280kg, slowly be added drop-wise to after mixing in the reaction kettle, 2 hours dropping time, 50 ℃ of controlled temperature, balanced reaction 15 hours, emptying are lowered the temperature to such an extent that modified imidazoline is subsequent use;
B, composite sensitization emulsifying agent composite: trolamine and polyoxyethylene nonylphenol ether is subsequent use by weight the mixed back that stirs of 1:1;
C, before using vinylformic acid-Propylene glycol monoacrylate, mix itself and hydrolyzed polymaleic anhydride subsequent use earlier;
Preparation: place reaction kettle to add the water stirring material of a, b, c, controlled temperature is 20-35 ℃, and the time is 50-70 minute, forms thick thing and promptly gets inhibiter.
2. inhibiter according to claim 1 is characterized in that: the color of the intermediate of modified imidazoline is a black, and nonirritant ammonia flavor does not dissolve in normal-temperature water, and acid number is less than 0.5mgKOH/g.
3. inhibiter according to claim 1 is characterized in that: product is 20-100mg/L to the dosage of the anti-hydrogen sulfide inhibition of pipeline and equipment.
4. inhibiter according to claim 1 is characterized in that: the batching of selecting raw material and synthesis modification tetrahydroglyoxaline for use is the commercially available prod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010582985 CN102344789B (en) | 2010-12-10 | 2010-12-10 | Hydrogen sulfide resistant corrosion inhibitor for oil and gas well pipeline |
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|---|---|---|---|
| CN 201010582985 CN102344789B (en) | 2010-12-10 | 2010-12-10 | Hydrogen sulfide resistant corrosion inhibitor for oil and gas well pipeline |
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| CN102344789A true CN102344789A (en) | 2012-02-08 |
| CN102344789B CN102344789B (en) | 2013-03-13 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| CN106188362A (en) * | 2016-07-18 | 2016-12-07 | 常州大学 | One class has inhibition polymer with viscosity reduction effect and preparation method thereof concurrently |
| CN106757046A (en) * | 2016-12-29 | 2017-05-31 | 中国石油天然气股份有限公司 | Corrosion inhibitor for sulfur-containing moisture conveying pipeline and preparation method thereof |
| CN107459984A (en) * | 2016-06-02 | 2017-12-12 | 中国石油大学(华东) | A kind of hydrogen sulfide corrosion inhibiter used in heavy crude heat extraction and preparation method thereof |
| CN107794531A (en) * | 2016-08-30 | 2018-03-13 | 中国石油天然气股份有限公司 | Carbon dioxide corrosion inhibitor for oil-gas well as preparation method and application thereof |
| CN110157402A (en) * | 2018-03-27 | 2019-08-23 | 德蓝水技术股份有限公司 | A kind of antibacterial anti-H of salt tolerant2S/CO2Corrosion inhibiter and preparation method thereof |
| CN110241425A (en) * | 2019-07-26 | 2019-09-17 | 威海翔泽新材料科技有限公司 | A kind of high-sulfur corrosion inhibiter for oil-gas gathering and transportation process |
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| CN1757797A (en) * | 2005-11-15 | 2006-04-12 | 中国石油天然气集团公司 | Corrosion inhibition neutralizer |
| CN101538718A (en) * | 2009-04-30 | 2009-09-23 | 西北工业大学 | Carbon steel restrainer and use method thereof |
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| CN101538718A (en) * | 2009-04-30 | 2009-09-23 | 西北工业大学 | Carbon steel restrainer and use method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| CN103881697B (en) * | 2014-03-14 | 2016-08-24 | 杭州央力科技有限公司 | A kind of imidazoline compound corrosion inhibitor and preparation method thereof |
| CN107459984A (en) * | 2016-06-02 | 2017-12-12 | 中国石油大学(华东) | A kind of hydrogen sulfide corrosion inhibiter used in heavy crude heat extraction and preparation method thereof |
| CN107459984B (en) * | 2016-06-02 | 2020-12-01 | 中国石油大学(华东) | Hydrogen sulfide corrosion inhibitor used in heavy oil thermal recovery and preparation method thereof |
| CN106188362A (en) * | 2016-07-18 | 2016-12-07 | 常州大学 | One class has inhibition polymer with viscosity reduction effect and preparation method thereof concurrently |
| CN106188362B (en) * | 2016-07-18 | 2019-02-12 | 常州大学 | One kind has the preparation method of the imidazoline polymer of inhibition and viscosity reduction effect concurrently |
| CN107794531A (en) * | 2016-08-30 | 2018-03-13 | 中国石油天然气股份有限公司 | Carbon dioxide corrosion inhibitor for oil-gas well as preparation method and application thereof |
| CN107794531B (en) * | 2016-08-30 | 2019-10-11 | 中国石油天然气股份有限公司 | Carbon dioxide corrosion inhibitor for oil-gas well as preparation method and application thereof |
| CN106757046A (en) * | 2016-12-29 | 2017-05-31 | 中国石油天然气股份有限公司 | Corrosion inhibitor for sulfur-containing moisture conveying pipeline and preparation method thereof |
| CN106757046B (en) * | 2016-12-29 | 2018-11-16 | 中国石油天然气股份有限公司 | Corrosion inhibitor for sulfur-containing moisture conveying pipeline and preparation method thereof |
| CN110157402A (en) * | 2018-03-27 | 2019-08-23 | 德蓝水技术股份有限公司 | A kind of antibacterial anti-H of salt tolerant2S/CO2Corrosion inhibiter and preparation method thereof |
| CN110241425A (en) * | 2019-07-26 | 2019-09-17 | 威海翔泽新材料科技有限公司 | A kind of high-sulfur corrosion inhibiter for oil-gas gathering and transportation process |
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| CN102344789B (en) | 2013-03-13 |
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Address after: 830013 Urumqi high tech Zone (new city) North Industrial Park, blue sky road, No. 216, No. Patentee after: DELAND WATER TECHNOLOGY Co.,Ltd. Address before: 830013, 216, Lantian Road, North Industrial Zone, hi tech Zone, the Xinjiang Uygur Autonomous Region, Urumqi Patentee before: XINJIANG DELAND Co.,Ltd. |
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