CN102746839B - Oil-soluble corrosion inhibitor, its preparation method - Google Patents
Oil-soluble corrosion inhibitor, its preparation method Download PDFInfo
- Publication number
- CN102746839B CN102746839B CN201110105529.6A CN201110105529A CN102746839B CN 102746839 B CN102746839 B CN 102746839B CN 201110105529 A CN201110105529 A CN 201110105529A CN 102746839 B CN102746839 B CN 102746839B
- Authority
- CN
- China
- Prior art keywords
- weight
- inhibiter
- oil
- preparation
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses an oil-soluble corrosion inhibitor, and its preparation method. The oil-soluble corrosion inhibitor comprises 30-70wt% of imidazolidinethione derivative of formula (1), 10-40wt% of alkyl phosphate of formula (2), and 10-50wt% of organic solvent, in the formula (1), R1 represents C6-C15 alkyl, R2 represents C6-C12 alkyl, R3 is R2 or H, and R4 is R2 or H. The corrosion inhibitor of the invention can inhibit the corrosion of metal surface in an environment containing H2S and CO2, has good metal surface film-forming property, can be used in high-temperature high-pressure oil wells or gathering and distribution system, and has good effect of protecting the surfaces of metal pipelines and devices.
Description
Technical field
The invention belongs to metallic corrosion and suppress field, more particularly relate to a kind of H of inhibition
2s/CO
2oil-soluble inhibitor of corrosion and preparation method thereof.
Background technology
In oilfield exploitation procedure, follow and in oil gas, contain a large amount of CO
2, H
2s and Cl
-deng corrosive medium, with the acting in conjunction of local water, condensation water, be to cause the one of the main reasons that in oil gas well mining and course of conveying, metallic substance destroys, shorten the work-ing life of oil-gas field equipment and gathering line.Along with the fast development of industrial gas oil, contain CO in recent years simultaneously
2, H
2the oil-gas field that the corrosive mediums such as S coexist occurs in succession, and the accident causing is thus more and more serious, and causes huge financial loss and serious societal consequence.At present mainly contain 3 kinds for the anti-corrosion measure of oil-gas field equipment and pipeline: select corrosion-resistant material, filling inhibiter and use inside coating or lining.Inhibiter is low owing to having cost, simple to operate, instant effect, and the feature such as applicable life-time service, therefore as a kind of economy, effectively and the metallic corrosion control method of highly versatile, be one of safeguard procedures the most frequently used in Oil/gas Well and gathering system.
CN1277240A discloses a kind of anti-CO that is contained sulfur derivatives, alkyl phosphate, alkynol, nonionogenic tenside and solvent composition by tetrahydroglyoxaline
2corrosion inhibitor.CN1818138A discloses a kind of control CO by oleic imidazolinone, thiocarbamide, Soxylat A 25-7 and solvent composition
2the inhibiter of corrosion.Above-mentioned inhibiter is mainly to suppress metallic substance to contain CO at oil-gas field
2cO in environment
2corrosion, but for H
2the etching problem of S does not relate to.CN1966774A discloses a kind of inhibition exploitation of oil-gas field being made up of tetrahydroglyoxaline quaternary ammonium compound, alkyl alcohol Soxylat A 25-7, fatty alcohol-polyoxyethylene ether and Virahol, has collected defeated process association H
2s and CO
2the inhibiter of corrosion, but in this inhibiter, the preparation of tetrahydroglyoxaline quaternary ammonium compound is loaded down with trivial details, and the corrosion mitigating effect of inhibiter more than 100 DEG C and under elevated pressures environment is poor.
Summary of the invention
The object of this invention is to provide a kind of H of inhibition
2s/CO
2oil-soluble inhibitor of corrosion and preparation method thereof, this inhibiter can contain H
2s and CO
2in environment, suppress the corrosion of metallic surface, and there is good metallic surface film forming properties.Inhibiter provided by the invention also can be used for, in the oil well or gathering line system under comparatively high temps and elevated pressures, the surface of metallic conduit and equipment all being had to good provide protection.
The invention provides a kind of oil-soluble inhibitor, it is characterized in that this inhibiter is made up of following component:
(A) imidazolidine 40 thione derivatives 30～70 % by weight
(B) alkyl phosphate 10～40 % by weight
(C) organic solvent 10～50 % by weight
In inhibiter gross weight, in inhibiter, the weight content of each component is 100 % by weight.
Wherein, the general structure of described imidazolidine 40 thione derivatives is suc as formula shown in (1):
In formula: R
1for C
6～C
15alkyl; The content of described imidazolidine 40 thione derivatives is preferably 40～60 % by weight, and in inhibiter gross weight, in inhibiter, the weight content of each component is 100 % by weight.
The general structure of described alkyl phosphate is suc as formula shown in (2):
In formula: R
2for C
6～C
12alkyl; R
3for R
2or H; R
4for R
2or H; The content of described alkyl phosphate is preferably 15～30 % by weight, and in inhibiter gross weight, in inhibiter, the weight content of each component is 100 % by weight.
Described organic solvent is C
6～C
10in aromatic hydrocarbons any one, preferred content is 15～40 % by weight, in inhibiter gross weight, in inhibiter, the weight content of each component is 100 % by weight.
The present invention also provides a kind of preparation method of described oil-soluble inhibitor, it is characterized in that comprising the steps:
(I) preparation of imidazolidine 40 thione derivatives:
Mixed in molar ratio by thiocarbamide and beta-hydroxyethyl quadrol according to 1: 1～1: 1.2, be warming up to 120～200 DEG C, be preferably 150～180 DEG C, react 2～8 hours, be preferably 3～5 hours, obtain 1-(2-hydroxyethyl)-2-imidazolidine thioketones, after being cooled to 50～90 DEG C according to thiocarbamide mol ratio be 1: 0.5～1: 2, being preferably 1: 0.8～mol ratio of 1: 1 adds saturated fatty acid, after adding at 100～200 DEG C, be preferably at the temperature of 120～160 DEG C, react 1～8 hour, be preferably 2～4 hours, after cooling, obtain general structure suc as formula the imidazolidine 40 thione derivatives shown in (1).
(II) alkyl alcohol and Vanadium Pentoxide in FLAKES are stirred according to the mixed in molar ratio of 1: 1～1: 1.5, be warming up to 40～80 DEG C, react 2～6 hours, obtain general structure suc as formula the alkyl phosphate shown in (2) after cooling.
(III) preparation of inhibiter:
Imidazolidine 40 thione derivatives prepared by step (I), alkyl phosphate prepared by step (II) mix according to described ratio with organic solvent and obtain inhibiter of the present invention.
Described saturated fatty acid in described preparation method is C
6～C
12alkyl monocarboxylic acid, described alkyl alcohol is C
6～C
12alkyl monocarbon alcohol.
Inhibiter provided by the invention can be used for containing H
2s and CO
2oil/gas Well, gathering line system and high salinity sewage in.Compared with prior art, have that consumption is few, inhibition efficiency is high, chemical stability and Heat stability is good, applied range, with low cost and manufacture the features such as easy.Inhibiter provided by the invention is at 20～150 DEG C, high containing H
2s and CO
2profit environment in, need only can effectively control H by 30～80mg/L
2s and CO
2to the corrosion of the metallic substance such as Oil/gas Well sleeve pipe and gathering line, corrosion inhibition rate is more than 90%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but these embodiment do not limit the scope of the invention.
Embodiment 1
Thiocarbamide and beta-hydroxyethyl quadrol are stirred according to the mixed in molar ratio of 1: 1.2, be warming up to 160 DEG C of reactions 4 hours; According to being 1: 1 with thiocarbamide mol ratio, mol ratio adds isocaprylic acid after following to be cooled to 80 DEG C, after adding, reacts 4 hours at the temperature of 150 DEG C, obtains imidazolidine 40 thione derivatives I after cooling.
Thiocarbamide and 3-hydroxyethylethylene diamine are stirred according to the mixed in molar ratio of 1: 1, be warming up to 150 DEG C of reactions 3 hours; Be cooled to 80 DEG C following after according to adding lauric acid (dodecylic acid) with the thiocarbamide mol ratio mol ratio of 1: 0.8, after adding, at the temperature of 180 DEG C, react 2 hours, obtain imidazolidine 40 thione derivatives II after cooling.
Thiocarbamide and beta-hydroxyethyl quadrol are stirred according to the mixed in molar ratio of 1: 1.1, be warming up to 150 DEG C of reactions 3 hours; Be cooled to 80 DEG C following after according to adding n-caprylic acid with the thiocarbamide mol ratio mol ratio of 1: 0.9, after adding, at the temperature of 180 DEG C, react 2 hours, obtain imidazolidine 40 thione derivatives III after cooling.
Embodiment 2
N-Octanol and Vanadium Pentoxide in FLAKES are stirred according to the mixed in molar ratio of 1: 1.5, be warming up to 50 DEG C, react 3 hours, obtain mixed alkyl phosphoric acid ester IV after cooling.
N-dodecanol and Vanadium Pentoxide in FLAKES are stirred according to the mixed in molar ratio of 1: 1, be warming up to 80 DEG C, react 5 hours, obtain mixed alkyl phosphoric acid ester V after cooling.
Embodiment 3
According in embodiment 1～2, make imidazolidine 40 thione derivatives I, II, III and mixed alkyl phosphoric acid ester IV, V respectively with C
6～C
10aromatic hydrocarbons is uniformly mixed and makes different inhibiter according to part by weight, as shown in table 1.
The composition of table 1 inhibiter
Embodiment 4
The invention provides inhibiter inhibition H in order to check
2s and CO
2the corrosion mitigating effect of corrosion, the present invention, with reference to oil and gas industry standard SY/T5273-2000 " oil field extracted water inhibiter method of evaluating performance ", adopts the assessment method simulated field environment of High Temperature High Pressure static state to evaluate the corrosion mitigating effect of inhibiter.The medium that experiment adopts is that total mineralization is 2.35 × 10
5mg/L, Cl content are 1.20 × 10
5the oil field oil-reservoir water of mg/L, experiment material is X52 steel.Experimental result is in table 2, table 3 and table 4.
The different inhibiter laboratory evaluation of table 2 data
As can be seen from Table 2, for H
2s, CO
2corrosion under environment, adds after the inhibiter of 30mg/L, and the corrodibility of corrosion system significantly reduces, the inhibiter of 50mg/L, and its corrosion inhibition rate is all more than 92%.
The different inhibiter laboratory evaluation of table 3 data
As shown in Table 3, at 80 DEG C, H
2s dividing potential drop is 0.5Mpa, CO
2dividing potential drop is in the medium solution of 2.5Mpa, adds after 40mg/L inhibiter, and the corrosion inhibition rate of 3 kinds of inhibiter all exceedes 94%; When the content of inhibiter is 80mg/L, the corrosion inhibition rate of 6 kinds of inhibiter is all more than 96%.
The different inhibiter laboratory evaluation of table 4 data
As shown in Table 4, at 120 DEG C, H
2s dividing potential drop is 0.5Mpa, CO
2dividing potential drop is in the medium solution of 2.5Mpa, and the corrosion inhibition rate of 6 kinds of inhibiter all exceedes 94%.
Claims (11)
1. an oil-soluble inhibitor, is characterized in that this inhibiter is made up of following component:
(A) imidazolidine 40 thione derivatives 30～70 % by weight
(B) alkyl phosphate 10～40 % by weight
(C) organic solvent 10～50 % by weight
In inhibiter gross weight, in inhibiter, the weight content sum of each component is 100 % by weight;
Wherein, the general structure of described imidazolidine 40 thione derivatives is suc as formula shown in (1):
R in formula
1for C
6～C
15alkyl;
The general structure of described alkyl phosphate is suc as formula shown in (2):
R in formula
2for C
6～C
12alkyl, R
3for R
2or H, R
4for R
2or H.
2. the oil-soluble inhibitor described in 1 as requested, is characterized in that: described organic solvent is C
6～C
10in aromatic hydrocarbons any one.
3. the oil-soluble inhibitor described in 1 or 2 as requested, is characterized in that: the content of described organic solvent is 15～40 % by weight, in inhibiter gross weight, in inhibiter, the weight content sum of each component is 100 % by weight.
4. the oil-soluble inhibitor described in 1 as requested, is characterized in that: the content of described imidazolidine 40 thione derivatives is 40～60 % by weight, in inhibiter gross weight, in inhibiter, the weight content sum of each component is 100 % by weight.
5. the oil-soluble inhibitor described in 1 as requested, is characterized in that: the content of described alkyl phosphate is 15～30 % by weight, in inhibiter gross weight, in inhibiter, the weight content sum of each component is 100 % by weight.
6. the preparation method of oil-soluble inhibitor described in claim 1, is characterized in that comprising the steps:
(I) preparation of imidazolidine 40 thione derivatives:
Mixed in molar ratio by thiocarbamide and beta-hydroxyethyl quadrol according to 1: 1～1: 1.2, be warming up to 120～200 DEG C, react 2～8 hours, be cooled to after 50～90 DEG C that mol ratio adds saturated fatty acid according to being 1: 0.5～1: 2 with thiocarbamide mol ratio, after adding at the temperature of 100～200 DEG C, react 1～8 hour, obtain if general structure is suc as formula the imidazolidine 40 thione derivatives as shown in (1) after cooling;
(II) alkyl alcohol and Vanadium Pentoxide in FLAKES are stirred according to the mixed in molar ratio of 1: 1～1: 1.5, be warming up to 40～80 DEG C, react 2～6 hours, obtain the alkyl phosphate as shown in structural formula (2) after cooling;
(III) preparation of inhibiter:
Imidazolidine 40 thione derivatives prepared by step (I), alkyl phosphate prepared by step (II) proportionally mix with organic solvent and obtain inhibiter.
7. preparation method according to claim 6, is characterized in that: described saturated fatty acid is C
6～C
12alkyl monocarboxylic acid, described alkyl alcohol is C
6～C
12alkyl monocarbon alcohol.
8. preparation method according to claim 6, is characterized in that: in described step (I), the temperature of reaction of thiocarbamide and beta-hydroxyethyl quadrol is 150～180 DEG C, and the reaction times is 3～5 hours.
9. according to the preparation method described in claim 6 or 8, it is characterized in that: while adding saturated fatty acid in described step (I), the mol ratio of saturated fatty acid and thiocarbamide is 1: 0.8～1: 1.
10. according to the preparation method described in claim 6 or 8, it is characterized in that: in described step (I), adding the temperature of reaction after saturated fatty acid is 120～160 DEG C, and the reaction times is 2～4 hours.
11. preparation methods according to claim 6, is characterized in that: described organic solvent is C
6～C
10in aromatic hydrocarbons any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110105529.6A CN102746839B (en) | 2011-04-22 | 2011-04-22 | Oil-soluble corrosion inhibitor, its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110105529.6A CN102746839B (en) | 2011-04-22 | 2011-04-22 | Oil-soluble corrosion inhibitor, its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102746839A CN102746839A (en) | 2012-10-24 |
| CN102746839B true CN102746839B (en) | 2014-06-18 |
Family
ID=47027340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110105529.6A Active CN102746839B (en) | 2011-04-22 | 2011-04-22 | Oil-soluble corrosion inhibitor, its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102746839B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119850B (en) * | 2013-04-24 | 2016-10-05 | 长江大学 | A kind of corrosion inhibiter in brine media and preparation method thereof |
| CN103450865B (en) * | 2013-08-28 | 2016-07-06 | 中国石油集团川庆钻探工程有限公司 | A kind of Oil-soluble hydrogen sulfide-proof corrosion inhibitor |
| US20160362598A1 (en) * | 2015-06-10 | 2016-12-15 | Baker Hughes Incorporated | Decreasing corrosion on metal surfaces |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277240A (en) * | 2000-06-21 | 2000-12-20 | 中国石油天然气总公司石油管材研究所 | Corrosion inhibitor resisting CO2 corrosion for oil field |
| CN101613598A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of inhibition H 2S/CO 2Corrosive inhibiter and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6084271A (en) * | 1983-10-13 | 1985-05-13 | Nippon Synthetic Chem Ind Co Ltd:The | 4,5-dihydroxyimidazolidinethione-2 and its preparation |
-
2011
- 2011-04-22 CN CN201110105529.6A patent/CN102746839B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277240A (en) * | 2000-06-21 | 2000-12-20 | 中国石油天然气总公司石油管材研究所 | Corrosion inhibitor resisting CO2 corrosion for oil field |
| CN101613598A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of inhibition H 2S/CO 2Corrosive inhibiter and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP昭60-84271A 1985.05.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102746839A (en) | 2012-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613598B (en) | Inhibitor restraining H2S/CO2 corrosion and preparation method thereof | |
| CN102942908B (en) | Water injected pitting-corrosion composite inhibitor and application thereof | |
| CN106609371B (en) | A kind of corrosion inhibiter and its preparation method and application | |
| CN103059825B (en) | Corrosion inhibitor for oil wells and preparation method | |
| CN107418548B (en) | Pyridine derivative and Mannich base composite high-temperature acidizing corrosion inhibitor | |
| CN102226281B (en) | Non-aldehyde acidification corrosion inhibitor and preparation method thereof | |
| CN102168272B (en) | Corrosion inhibitor for sour oil and gas fields | |
| CN102746839B (en) | Oil-soluble corrosion inhibitor, its preparation method | |
| CN105483708B (en) | Contain H suitable for oil gas field2S/CO 2Corrosion inhibiter of corrosive environment feed-line and preparation method thereof | |
| CN102051622A (en) | Carbon steel acidizing corrosion inhibitor | |
| CN105568292A (en) | Alkyl pyridinium quaternary ammonium salt corrosion inhibitor used for inhibiting carbon dioxide corrosion and preparation method thereof | |
| CN102747374B (en) | Oil-soluble corrosion inhibitor, its preparation method and application | |
| CN102953064B (en) | Mannich base corrosion-retarding neutralizer and preparation method thereof | |
| CN105239076A (en) | Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof | |
| CN107699900B (en) | CO2 corrosion inhibitor for gathering and transportation pipelines of oil and gas fields and preparation method thereof | |
| CN102586782B (en) | Corrosion inhibitor and preparation and application thereof | |
| CN114214052A (en) | Compound corrosion inhibitor for high-density completion fluid in micro-sulfur-containing environment and preparation method and application thereof | |
| CN100560801C (en) | A kind of water-soluble high-temperature organic acid inhibitor and preparation method thereof and using method | |
| CN102268677A (en) | Corrosion inhibitor for inhibiting H2S/CO2 corrosion and preparation method thereof | |
| CN102888246B (en) | Corrosion-inhibition anti-coking agent for furfural refining device | |
| CN103897681B (en) | A kind of oil gas field corrosion inhibiter and preparation method thereof | |
| CN105238379B (en) | A kind of long-acting corrosion inhibiter of acidification of gas well and its preparation method and application method | |
| CN102220170B (en) | Corrosion inhibitor for hydrogenation unit and preparation method thereof | |
| CN101824355A (en) | Machinery seal vapor phase anti-rust and preparation method thereof | |
| CN102559167A (en) | Novel preparation method of schiff base oil well acidification corrosion inhibitor and application of preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |