CN102344789B - 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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- CN102344789B CN102344789B CN 201010582985 CN201010582985A CN102344789B CN 102344789 B CN102344789 B CN 102344789B CN 201010582985 CN201010582985 CN 201010582985 CN 201010582985 A CN201010582985 A CN 201010582985A CN 102344789 B CN102344789 B CN 102344789B
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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 screening and the preparation of technology, especially inhibiter of the anti-hydrogen sulfide inhibition of Oil/gas Well pipeline 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 apparent 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 such as 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 rational 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. Dong Ze China wait the people utilize computer-controlled potentiodynamic method studied the oil soluble imidazolines to carbon steel at slightly acidic H
2Corrosion inhibition in the S aqueous solution; 2. the people such as sieve Zhe beautiful woman has studied naphthenic acid imidazoline inhibiter HM, HMO through obtaining through ethoxylation and quaterisation modification at H
2Good corrosion inhibition is arranged in the S medium; 3. the 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 from 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 pipeline and equipment, had reduced again the manufacturing cost of former inhibiter, 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 object of the present invention is achieved like this: a kind of inhibiter of the anti-hydrogen sulfide for Oil/gas Well pipeline and equipment, raw material is prepared with parts by weight, is comprised of modified imidazoline 40-60 part, vinylformic acid-Propylene glycol monoacrylate 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 reactor, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes; 150 ℃ of lower maintenances 2.5 hours, be warming up to 190 ℃, kept 30 minutes, vacuum tightness is-0.015MPA; Then slowly be warming up to 230 ℃, vacuum keep at-0.018MPA, was reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
With the intermediate modification: add ethanol 100kg, intermediate 385kg to reactor and stir, be warming up to 40 ℃; 235kg dithiocarbonic anhydride is joined in the ethanol of 280kg, mix rear slowly being added drop-wise in the reactor, time for adding 2 hours, the control temperature 50 C, balanced reaction 15 hours, emptying are lowered the temperature to such an extent that modified imidazoline is for subsequent use;
B, composite sensitization emulsifying agent composite: with trolamine and polyoxyethylene nonylphenol ether by weight 1:1 mixed stir rear for subsequent use;
C, before using vinylformic acid-Propylene glycol monoacrylate, mix itself and hydrolyzed polymaleic anhydride for subsequent use first;
Preparation: place reactor to add the water stirring material of a, b, c, the control temperature is 20-35 ℃, and the time is 50-70 minute, forms thick thing and namely 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 for the dosage of the anti-hydrogen sulfide inhibition of pipeline and equipment.
Described inhibiter, the batching of selecting raw material and synthesis modification tetrahydroglyoxaline 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 by polar group on its molecule, make it be adsorbed on the metallic surface, change so on the one hand charge distribution and the interfacial property of metallic surface, 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 in the metallic surface one deck hydrophobicity protective membrane, 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 thioureido-imidazoline, 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.
The action principle that product of the present invention is compound to the sensitization emulsifying agent: emulsifying agent shared content in composite corrosion inhibitor exceeds several times than its content shared in common oil in water emulsion, so that the liquid phase dielectric hydrophobic substance of emulsification still can keep stable relatively in 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 unstability of emulsion dispersion, promote that medicament is separated out in the preferential unstability of metal interface, automatic absorbing forms the hydrophobic liquid film of high resistant in the metallic surface, the performance corrosion inhibition.
The 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 inhibiter is present in the water body with the metastable condition of high dispersing, and can with preferentially separate out in this solid-liquid interface (or giving hot interface) unstability after the metallic surface contacts, automatic absorbing forms the high resistant hydrophobic membrane in the metallic surface, so that inhibiter reaches very high numerical value at the partial concn of solid-liquid interface, make drug effect be surpassed performance, and then save to greatest extent medication, add the effect of modified imidazoline agent in this liquid film, just can suppress most effectively the generation of the corrosion of metal, show technical progress.
Embodiment
Embodiment 1
Raw material is prepared with parts by weight, is comprised of 40 parts of 50 parts of modified imidazolines, 5 parts of vinylformic acid-Propylene glycol monoacrylates, 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 reactor, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes, 150 ℃ of lower maintenances 2.5 hours, be warming up to 190 ℃, kept 30 minutes, make vacuum tightness be-0.015MPA; Then slowly be warming up to 230 ℃, vacuum keep at-0.018MPA, was reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
Intermediate modification with the upper step: add ethanol 100kg, intermediate 385kg to reactor and stir, 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 reactor, time for adding is 2 hours, and temperature is controlled at 50 ℃; Balanced reaction 15 hours, the emptying modified imidazoline of lowering the temperature to get;
B, composite sensitization emulsifying agent preparation: trolamine and polyoxyethylene nonylphenol ether are stirred and get final product by weight 1:1 is mixed;
C, vinylformic acid-Propylene glycol monoacrylate is added in the hydrolyzed polymaleic anhydride and to add again after mixing first;
Total preparation: place reactor to add the water stirring material of a, b, c, the control temperature is 35 ℃, and the time is 60 minutes, forms thick thing and namely 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 reactor after disposing respectively, stir, time is 60 minutes, the control 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 reactor after disposing respectively, add 30 parts of stirrings of water, time is 50 minutes, the control temperature is 25 ℃, forms thick thing and gets product, and the step of its a, b, c is with embodiment 1.
The present invention verifies the performance of its product by following test data.
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 sees Table.
Learnt by upper 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; Hang the A3 steel disc for the monitoring lacing film in pipeline, take out steel disc after three months, erosion rate is 0.01517mm/a.
Claims (4)
1. inhibiter that is used for the anti-hydrogen sulfide of Oil/gas Well pipeline and equipment, it is characterized in that: raw material is prepared with parts by weight, is comprised of modified imidazoline 40-60 part, vinylformic acid-Propylene glycol monoacrylate 3-7 part, hydrolyzed polymaleic anhydride 3-7 part, composite sensitization emulsifying agent 35-45 part; Its preparation method is as follows:
The preparation of a, modified imidazoline: add lauric acid 676kg, diethylenetriamine 260kg to reactor, stir and be warming up to 140 ℃, vacuumize below the 0.01MPa after 20 minutes; 150 ℃ of lower maintenances 2.5 hours, be warming up to 190 ℃, kept 30 minutes, vacuum tightness is-0.015MPa; Then slowly be warming up to 230 ℃, vacuum keep at-0.018MPa, was reacted 4 hours, cooling is below 70 ℃, and discharging gets intermediate;
With the intermediate modification: add ethanol 100kg, intermediate 385kg to reactor and stir, be warming up to 40 ℃; 235kg dithiocarbonic anhydride is joined in the ethanol of 280kg, mix rear slowly being added drop-wise in the reactor, time for adding 2 hours, the control temperature 50 C, balanced reaction 15 hours, emptying are lowered the temperature to such an extent that modified imidazoline is for subsequent use;
B, composite sensitization emulsifying agent composite: with trolamine and polyoxyethylene nonylphenol ether by weight 1:1 mixed stir rear for subsequent use;
C, before using vinylformic acid-Propylene glycol monoacrylate, mix itself and hydrolyzed polymaleic anhydride for subsequent use first;
Preparation: place reactor to add the water stirring material of a, b, c, the control temperature is 20-35 ℃, and the time is 50-70 minute, forms thick thing and namely gets inhibiter.
2. inhibiter according to claim 1, it is characterized in that: the color of the intermediate of modified imidazoline is 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, it is characterized in that: described inhibiter is 20-100mg/L for the dosage of the anti-hydrogen sulfide inhibition of pipeline and equipment.
4. inhibiter according to claim 1, it is characterized in that: the batching of selecting raw material and synthesis modification tetrahydroglyoxaline is the commercially available prod.
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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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| 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 |
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| 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 |
| 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 |
| 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 |
| 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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| DE3119376A1 (en) * | 1981-05-15 | 1982-12-02 | Basf Ag, 6700 Ludwigshafen | INHIBITORS AGAINST THE CORROSION OF H (DOWN ARROW) 2 (DOWN ARROW) S AND CO (DOWN ARROW) 2 (DOWN ARROW) IN WATER-IN-OIL EMULSIONS |
| CN1309869C (en) * | 2005-11-15 | 2007-04-11 | 中国石油天然气集团公司 | Corrosion inhibition neutralizer |
| CN101538718B (en) * | 2009-04-30 | 2010-12-01 | 西北工业大学 | Carbon steel restrainer and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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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. |