CN104232042A - Polyphenyl polycyclic-imidazoline corrosion inhibitor - Google Patents
Polyphenyl polycyclic-imidazoline corrosion inhibitor Download PDFInfo
- Publication number
- CN104232042A CN104232042A CN201410401516.7A CN201410401516A CN104232042A CN 104232042 A CN104232042 A CN 104232042A CN 201410401516 A CN201410401516 A CN 201410401516A CN 104232042 A CN104232042 A CN 104232042A
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- Prior art keywords
- corrosion
- imidazoline
- many
- corrosion inhibitor
- phenyl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D233/16—Radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a polyphenyl polycyclic-imidazoline corrosion inhibitor, and particularly relates to a corrosion inhibitor with an inhibition effect on the corrosion of acid gases such as CO2 and H2S, belonging to the technical field of oilfield chemicals design. The corrosion inhibitor is characterized by having the following chemical structural formula as shown in the specification, wherein R is C17H33, C15H29 and C13H25. In saturated CO2-containing simulated formation water, the corrosion inhibition rate of the polyphenyl polycyclic-imidazoline corrosion inhibitor disclosed by the invention can reach 93%, which is higher than that of a monocyclic imidazoline corrosion inhibitor under the condition that the addition amounts of the two corrosion inhibitors are same; and in H2S dynamic corrosion experiments, the corrosion inhibition rate is 81%, and the corrosion inhibitor disclosed by the invention has a relatively strong inhibition effect on H2S corrosion. The corrosion inhibitor disclosed by the invention is simple in production process, mild in reaction conditions, easy to use, and wide in applicability.
Description
Technical field:
The present invention relates to a kind of many phenyl many rings imidazoline inhibitors, particularly a kind of to CO
2, H
2s sour gas corrosion has inhibiting inhibiter, belongs to Oilfield Chemicals design field.
Background technology:
In the performance history of Chinese large-sized acid gas field, the protection of pit shaft and surface pipeline network corrosion is the primary major issue solved.And cause the major cause of pit shaft and ground metal piping corrosion to be due to CO
2and H
2after the sour gas such as S are water-soluble, dissociate H
+, the corrosion of metal pipe material is caused by hydrogen depolarization effect.Due to CO
2the aqueous solution has the corrodibility stronger than hydrochloric acid under equal pH, and H
2s is not only obvious to metal pipe material corrosive nature, and the hydrogen that corrosion produces is extremely strong to tubing matrix destructiveness, usually causes sulfide stress cracking (SSC), hydrogen-induced crack and hydrogen blistering etc., thus greatly strengthen sour gas (CO
2, H
2s) to corrosion failure speed and the degree of pit shaft and ground metal pipe network.
Used inhibiter is form adsorption film by it in metallic surface absorption to suppress corrosion mostly, belongs to adsorbed film type inhibiter.The absorption of monocycle imidazoline inhibitor on metal pipe material surface as conventional only belongs to monodentate ligand surface complexes, and its adsorptive power not by force and easily De contamination occurs, effectively can not stop corrosive medium and metal pipe material generation corrosion reaction.
Accordingly, the invention provides a kind of many electron riches phenyl ring, novel corrosion inhibitor that many rings tetrahydroglyoxaline (6 phenyl ring, 4 tetrahydroglyoxaline rings) forms many adsorption centers.This inhibiter can form multinuclear coordination surface title complex in metal pipe material surface adsorption, its Spontaneous adsorption energy force rate monocycle tetrahydroglyoxaline by force and not easily De contamination, this inhibiter is also containing multiple hydrophobic grouping simultaneously, the hydrophobic protective membrane of absorption inhibiter can be formed on metal pipe material surface, under sour gas environment, better preservative activity is played to pit shaft and surface pipeline network metal pipe material.
Summary of the invention:
In order to overcome the deficiencies in the prior art part; the object of the present invention is to provide a kind of many phenyl many rings imidazoline inhibitors; the hydrophobic inhibition protection film of multinuclear Coordination Adsorption type is formed by its peculiar many electron riches phenyl ring, many rings tetrahydroglyoxaline; overcome the indifferent and deficiency that is easily De contamination of existing monocycle imidazoline inhibitor Spontaneous adsorption, especially to CO
2, H
2s sour gas corrosion has restraining effect, makes it easier and adsorbs in metallic surface and not easily De contamination occur, thus more effectively suppress CO
2, H
2s etc. are to the corrosion of pit shaft and surface pipeline network metal pipe material.
The present invention realizes above-mentioned purpose by following technical solution.
(1) preparation of Fourth Ring tetrahydroglyoxaline
Generate Fourth Ring tetrahydroglyoxaline with 1.0G polyamide-amide and long-chain fat acid-respons, its chemical equation is as follows:
Wherein: longer chain fatty acid is: RCOOH; R is: C
17h
33, C
15h
29, C
13h
25;
(2) preparation of many phenyl many rings imidazoline quaternary ammonium salts
By Benzyl Chloride and Fourth Ring tetrahydroglyoxaline quaterisation, synthesize a kind of many phenyl many rings imidazoline quaternary ammonium salts, i.e. many phenyl many rings imidazoline inhibitors (MPMII) of the present invention, its chemical equation is as follows:
Wherein R is: C
17h
33, C
15h
29, C
13h
25.
The present invention compared with prior art, has following beneficial effect:
1, saturated CO is being contained
2add 200mg/L many phenyl many rings imidazoline inhibitors of the present invention in simulated formation water, corrosion inhibition rate can reach 93%, higher than the corrosion inhibition rate of the monocycle imidazoline inhibitor SRH-02 of identical dosage.
2, at H
2in the experiment of S Dynamic Corrosion, the corrosion inhibition rate of many phenyl many rings imidazoline inhibitors of the present invention is 81%, to H
2s corrosion has stronger restraining effect.
3, multiple adsorption center is had.When many phenyl many rings imidazoline inhibitor (MPMII) dosages are not more than 200mg/L, in metallic surface, absorption belongs to monolayer adsorption, and adsorption free energy Δ G=-39.53kJ/mol, belongs to spontaneous process.
4, this product processes is simple, and reaction conditions is gentle, and product is easy to use, and suitability is wide.
Accompanying drawing illustrates:
Fig. 1 is adsorption structure schematic diagram centered by atom N.
Fig. 2 is adsorption structure schematic diagram centered by phenyl ring.
Embodiment:
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
1, the preparation of 1.0G polyamide-amide
The polyamide-amide of a mol 0.5G and 6a ~ 8a mol methyl alcohol are joined in the there-necked flask of band magnetic agitation, reflux condensing tube and thermometer, under 20 ~ 40 DEG C of conditions, drip 8a ~ 16a mol diethylenetriamine, after reaction 24h ~ 48h, underpressure distillation is carried out at 70 ~ 80 DEG C, removing methyl alcohol and excessive diethylenetriamine, obtain 1.0G polyamide-amide.
2, the preparation of Fourth Ring tetrahydroglyoxaline
In a mol longer chain fatty acid (unsaturated alkyl lipid acid), add azeotropic agent (accounting for the 15-35% of reactant volume) dimethylbenzene, oil bath is heated and is stirred, slow dropping 3a ~ 5a mol 1.0G polyamide-amide, dropwises and is warming up to 140 ~ 160 DEG C, reaction 4h ~ 6h, then be rapidly heated to 180 ~ 220 DEG C, cyclisation 3h ~ 6h, steams remaining dimethylbenzene, obtains Fourth Ring tetrahydroglyoxaline.
3, the preparation of hexaphenyl Fourth Ring imidazoline quaternary ammonium salt
In the tetrahydroglyoxaline of a mol Fourth Ring, slowly drip 6a-7a mol Benzyl Chloride, and constantly stir, at 80 ~ 110 DEG C, be incubated 4h ~ 6h after dropwising, cool to obtain hexaphenyl Fourth Ring imidazoline quaternary ammonium salt, be i.e. many phenyl many rings imidazoline inhibitors (MPMII).
Embodiment 2:
The effect example of a kind of many phenyl many rings imidazoline inhibitors of the present invention:
1, saturated CO is being contained
2in simulated formation water (simulated formation water ion content is in table 1), add the many phenyl of 200mg/L many rings imidazoline inhibitor, corrosion inhibition rate can reach 93%, higher than the corrosion inhibition rate (corrosion inhibition rate 85.7%) of identical dosage list tetrahydroglyoxaline ring inhibiter SRH-02.As shown in table 2.
Table 1: simulated formation water ion content
Table 2: many phenyl many rings imidazoline inhibitor dosages are to saturated CO
2the corrosion mitigating effect of simulated formation water
2, at H
2in the experiment of S Dynamic Corrosion (simulated formation water ion content is in table 3), rotating speed 60r/min, P
h2S=0.4MPa, etching time 24h, corrosion temperature 90 DEG C, the many phenyl of 200mg/L many rings imidazoline inhibitor (MPMII) corrosion inhibition rate is 81%, to H
2s corrosion has stronger restraining effect.
Table 3 simulated formation water ion content
3, multiple adsorption center is had.When many phenyl many rings imidazoline inhibitor (MPMII) dosages are not more than 200mg/L, in metallic surface, absorption belongs to monolayer adsorption, and adsorption free energy Δ G=-39.53kJ/mol, belongs to spontaneous process.Suction type is as follows:
A () adsorbs centered by atom N:
As shown in Figure 1:
Wherein R is: C
17h
33, C
15h
29, C
13h
25;
R
1for:
B () adsorbs centered by phenyl ring
As shown in Figure 2:
Wherein R is: C
17h
33, C
15h
29, C
13h
25;
R
1for:
C () be chelating absorption centered by electron rich group:
Meanwhile, the adsorption center in inhibitor molecular also can with anodic corrosion product Fe
2+coordination, in the large π key that in inhibiter, phenyl ring is formed and hydrophobic chain electron rich unsaturated link(age) can and Fe
2+coordination forms huge legendary turtle compound, effectively improves stability and the compactness extent of adsorption film, can suppress negative electrode and the anodic process of corrosion.With Fe
2+it is as follows that coordination forms huge legendary turtle laminate structures:
Wherein R is: C
17h
33, C
15h
29, C
13h
25;
R
1for:
Claims (2)
1. the many rings of phenyl a more than imidazoline inhibitor, is characterized in that having following chemical structural formula:
Wherein R is: C
17h
33, C
15h
29, C
13h
25.
2. the preparation method of a kind of many phenyl many rings imidazoline inhibitors as claimed in claim 1, is characterized in that:
(1) preparation of Fourth Ring tetrahydroglyoxaline
Generate Fourth Ring tetrahydroglyoxaline with 1.0G polyamide-amide and long-chain fat acid-respons, its chemical equation is as follows:
Wherein: longer chain fatty acid is: RCOOH; R is: C
17h
33, C
15h
29, C
13h
25;
(2) preparation of many phenyl many rings imidazoline quaternary ammonium salts
By Benzyl Chloride and Fourth Ring tetrahydroglyoxaline quaterisation, synthesize a kind of many phenyl many rings imidazoline quaternary ammonium salts, i.e. many phenyl many rings imidazoline inhibitors of the present invention, its chemical equation is as follows:
Wherein R is: C
17h
33, C
15h
29, C
13h
25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410401516.7A CN104232042A (en) | 2014-08-15 | 2014-08-15 | Polyphenyl polycyclic-imidazoline corrosion inhibitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410401516.7A CN104232042A (en) | 2014-08-15 | 2014-08-15 | Polyphenyl polycyclic-imidazoline corrosion inhibitor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045499A (en) * | 2021-03-16 | 2021-06-29 | 中国科学院理化技术研究所 | Asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, and preparation and application thereof |
| CN116023920A (en) * | 2022-11-11 | 2023-04-28 | 天津大港油田滨港集团博弘石油化工有限公司 | Environment-friendly tetracyclic imidazoline solid corrosion inhibitor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN103723843A (en) * | 2013-12-13 | 2014-04-16 | 中国石油天然气股份有限公司 | Novel corrosion and scale inhibitor and preparation method thereof |
-
2014
- 2014-08-15 CN CN201410401516.7A patent/CN104232042A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN103723843A (en) * | 2013-12-13 | 2014-04-16 | 中国石油天然气股份有限公司 | Novel corrosion and scale inhibitor and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 刘军海: "咪唑啉型两性表面活性剂合成及应用研究进展", 《中国洗涤用品工业》 * |
| 朱镭: "咪唑啉缓蚀剂的研究与应用进展", 《材料保护》 * |
| 樊国栋: "新型咪唑啉缓蚀剂的合成及性能评价", 《精细石油化工》 * |
| 王大喜: "取代基咪唑啉分子结构与缓蚀性能的理论研究-咪唑啉分子与铁原子化学吸附位能曲线的量子化学计算", 《石油学报（石油加工）》 * |
| 王腾飞: "树状咪唑啉缓蚀剂的制备与应用", 《精细石油化工》 * |
| 胡祯: "《新型高分子合成与制备工艺》", 30 May 2014, 哈尔滨工业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045499A (en) * | 2021-03-16 | 2021-06-29 | 中国科学院理化技术研究所 | Asymmetric long-chain alkyl benzyl imidazoline polyethylene long-chain alkylamide cationic compound, and preparation and application thereof |
| CN116023920A (en) * | 2022-11-11 | 2023-04-28 | 天津大港油田滨港集团博弘石油化工有限公司 | Environment-friendly tetracyclic imidazoline solid corrosion inhibitor and preparation method thereof |
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Application publication date: 20141224 |