CN1277240A - Corrosion inhibitor resisting CO2 corrosion for oil field - Google Patents
Corrosion inhibitor resisting CO2 corrosion for oil field Download PDFInfo
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- CN1277240A CN1277240A CN 00109687 CN00109687A CN1277240A CN 1277240 A CN1277240 A CN 1277240A CN 00109687 CN00109687 CN 00109687 CN 00109687 A CN00109687 A CN 00109687A CN 1277240 A CN1277240 A CN 1277240A
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- tetrahydroglyoxaline
- alkyl
- inhibiter
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Abstract
The corrosion inhibitor includes sulfur-containing imidazoline derivative 25-40wt%, alkyl phosphate 20-30wt%, alkynol 5-15wt%, non-ionic surfactant 10-20wt% and solvent 20-30wt%. It can form one layer of efficient protecting film on the surface of metal pipe and equipment to prevent the corrosion of highly mineralized CO2 containing sewage to the surface. It may be used in oil well with relatively high temperature and pressure and other industrial equipment and has the features of less consumption, high efficiency,easy preparation and low cost.
Description
The present invention relates to the aseptic technic of metallic substance, particularly relate to the novel anti CO that is applicable to the oil field
2Corrosive inhibiter and preparation method thereof.
As everyone knows, CO
2Corrosion is the form of corrosion that extremely strong general corrosion of a kind of destructive force and local corrosion are laid equal stress on; And CO
2One of injection gas in usually adopting as associated gas, three or component of Sweet natural gas extensively are present among the oil gas.This corrosion is relevant with in situ temperature and pressure factor usually, and the tubing and casing that it causes and the failure consequence of line of pipes are very serious.For example, in May, 1971, the Sichuan prestige became pipeline to get over the small stream section because the CO in the desulfurizing and purifying gas
2And remaining H
2The corrosion failure of S sets off an explosion, burns, injures and deaths 24 people.1975, alpha's platform in the Ekofisk oil field of oil field, North Sea Norway one side was because height contains CO in the crude oil
2And chlorion, make 10 3/4 inches APIX50 high temperature standpipe come into operation only two months, just corrode thin as a piece of paper page or leaf, set off an explosion, burning and human casualty accident.A bite gas well of refined carat of gas condensate field of China is under arms after 10 months, because CO
2Corrosion cause oil pipe perforation blowout, caught fire 76 days, direct economic loss reaches more than 3,000 ten thousand yuan, indirect economic loss is several times as much as this number.In addition, because CO
2Bore a hole well, sucker rod of corrosion and the oil pipe that causes breaks etc. of common occurrence especially.These pernicious malicious events not only can cause enormous economic loss, and can bring serious societal consequence.
In the prior art, the oil field is suppressing CO
2In the safeguard procedures to pipeline and equipment corrosion, mainly take to change methods such as material and filling inhibiter.Because chromium stainless steel costs an arm and a leg, change carbon steel and can not fundamentally solve etching problem again, therefore, the filling inhibiter is used as one of prefered method, is widely used in the oil-gas mining process.A kind of 17 alkenyl imidazoline corrosion inhibitor for oil field (CN1052151A) can be used for containing CO
2Oil-gas field, but be mainly used in the defeated and sewage works of collection, and its usage quantity is very big, use cost height, efficient are low.Adopt lauryl imidazoline derivative and ethyl phosphorothioic acid ester to press the certain mol proportion hybrid reaction, also can make ID-1 inhibiter (CN1043534A), but this inhibiter can only use under the lower situation of temperature, and the product smell is bigger.
The object of the invention is to develop a kind of novel anti CO
2The corrosive inhibiter makes it form the effective protective membrane of one deck at metallic conduit and equipment surface, prevents to contain CO
2High salinity sewage the metallic surface is corroded.Inhibiter of the present invention can be used in the oil well of comparatively high temps and elevated pressures, and in suitability for industrialized production and application process, has that consumption is few, efficient is high, manufacturing is easy and characteristics such as with low cost.
The present invention relates to a kind of oil field novel anti CO
2Corrosion inhibitor, this inhibiter belong to oily molten aqueous dispersion type, are a kind of alternate and interface bonded mixing and absorption film inhibitors.Described inhibiter component comprises:
(A) 25-40% (weight) tetrahydroglyoxaline contains sulfur derivatives,
(B) 20-30% (weight) alkyl phosphate,
(C) 5-15% (weight) alkynol,
(D) 10-20% (weight) nonionogenic tenside, and
(E) 20-30% (weight) solvent.
Wherein, alkynol is C
3-C
6Alkynol; Nonionogenic tenside is aliphatic alcohol polyethenoxy base ether or alkylphenol-polyethenoxy base ether; Solvent is ethanol, Virahol or ethylene glycol.
The general structure that tetrahydroglyoxaline contains sulfur derivatives is:
Wherein, R
1Be C
12-C
20Alkyl or alkenyl;
R
2, R
3Be C
0-C
5Alkyl or alkenyl.
It is synthetic by following method that tetrahydroglyoxaline in the inhibiter of the present invention contains sulfur derivatives: with lipid acid, part polyamines and take water solvent (as toluene or dimethylbenzene) join simultaneously have stir and the reactor of water distilling apparatus in, after reacting 3 hours under 145 ℃～175 ℃, in reactor, drip another part polyamines again, continue to heat up, reacted 2-5 hour down in 240 ℃～260 ℃, this moment, the acid number of reaction product was lower than 2.0mgKOH/g.Be cooled to below 100 ℃, again to wherein adding substituting group thiocarbamide and alkanol, 130 ℃～155 ℃ condensation reaction 4-6 hour, obtain tetrahydroglyoxaline after the cooling and contain sulfur derivatives.
The general structure of alkyl phosphate is:
Wherein, R
4Be C
8-C
14Alkyl;
R
5=R
4Or H;
R
6=R
4Or H.
Alkyl phosphate in the inhibiter of the present invention is synthetic by following method: with alkyl alcohol and P
2O
5Join respectively in the reactor that has agitator and thermometer, under agitation slowly heat up, react 3-5 hour postcooling down in 40 ℃～70 ℃ and obtain the mixed alkyl phosphoric acid ester.
The invention still further relates to the preparation method of above-mentioned inhibiter.This method comprises: aforesaid method synthetic tetrahydroglyoxaline is contained sulfur derivatives, alkyl phosphate and alkynol, nonionogenic tenside and solvent according to described mixed.
Product provided by the invention contains CO at 50-120 ℃, height
2The profit environment in, need only 30-200ppm, can effectively control CO
2To the corrosion of carbon steel equipment, corrosion inhibition rate reaches more than 90%.
Embodiment
In order further to set forth oil field of the present invention novel anti CO
2Corrosion inhibitor and preparation method thereof, the present invention has provided following several embodiment; But these embodiment are used for limiting the scope of the invention by any way.
Embodiment 1 and 2 has provided the employing different material respectively and has prepared the anti-CO of the present invention
2The method of corrosion inhibitor; Embodiment 3 provides the application example of described inhibiter.
Embodiment 1
123g Palmiticacid, 38g diethylenetriamine and 20g dimethylbenzene are joined in the reactor that has stirring and water distilling apparatus simultaneously, reacted 3 hours down, be warming up to about 180 ℃ rapidly, in reactor, drip the 38g diethylenetriamine again at 165 ℃; Continue to heat up, reacted 4 hours down in 240 ℃～260 ℃, obtain the tetrahydroglyoxaline intermediate, its acid number is lower than 2.0mgKOH/g.
Above-mentioned product temperature is cooled to below 100 ℃, in reactor, adds 75g thiocarbamide and 100g propyl carbinol, under 130～155 ℃, carry out condensation reaction 4 hours, obtain brown thick 1-(two thiocarbamides)-ethyl-2-pentadecyl tetrahydroglyoxaline after the cooling.
With 130g C
8Pure and mild 50g P
2O
5Join in another reactor that has agitator and thermometer, under agitation condition, slowly heat up, reacted 5 hours down, obtain mixed alkyl phosphoric acid ester (wherein containing phosphoric acid one monooctyl ester and dioctylphosphoric acid ester) after the cooling in 40 ℃～70 ℃.
With weight ratio is that 1-(two thiocarbamides)-ethyl-2-pentadecyl tetrahydroglyoxaline of 40%, 20% mixed alkyl phosphoric acid ester, 10% propiolic alcohol, 10% octylphenol polyethylene oxyethylene group ether and 20% Virahol mix mutually, stir, make the anti-CO of oily molten aqueous dispersion type
2Corrosion inhibitor.
Embodiment 2
According to method similar to Example 1, the inhibiter of preparation present embodiment.
Make the tetrahydroglyoxaline intermediate by 100g oleic acid, 55g diethylenetriamine and 15g dimethylbenzene; Add 70g propenyl thiocarbamide and 90g n-hexyl alcohol, reaction makes 1-(diallyl thiocarbamide)-ethyl-2-17 alkenyl imidazolines; By 140g n-dodecanol and 35g P
2O
5Reaction makes mixed alkyl phosphoric acid ester (wherein containing phosphoric acid one dodecyl ester and di(2-ethylhexyl)phosphate dodecyl ester); 1-with 30% (diallyl thiocarbamide)-ethyl-2-17 alkenyl imidazolines, 25% mixed alkyl phosphoric acid ester, 10% propiolic alcohol, 15% aliphatic acid polyethenoxy base ether and 20% Virahol mix mutually, make anti-CO
2Corrosion inhibitor.
Embodiment 3
In order to check this inhibiter to suppress CO
2The corrosive action effect, the present invention has adopted high temperature static and the dynamic two kinds of assessment method simulated field environment of High Temperature High Pressure that its corrosion mitigating effect is estimated.The medium total mineralization that test is adopted is 2.29 * 10
5Mg/l, Cl
-Content is 1.1 * 10
5The oil field oil-reservoir water of mg/l, material are tubing and casing such as oil field N80, P110 commonly used, C90.
Table 1 has provided this inhibiter under the different concns at 90 ℃, CO
2Dividing potential drop is the evaluation result in the medium solution of 0.1Mpa, and test period is 72 hours, and material is the N80 steel.
Static test result under table 1 different concns
Table 2 provided this inhibiter under differing temps, CO
2Dividing potential drop is that 3.0Mpa, rotating speed are the dynamic evaluation result in the medium solution of 1.5m/s, and test period is 72 hours, and density of corrosion inhibitor is 200ppm.
Dynamic evaluation result under table 2 differing temps
| Temperature (℃) | Material | Erosion rate (mm/a) | Corrosion inhibition rate (%) | |
| Blank | Add inhibiter (200ppm) | |||
| ????50 | ??N80 | ????12.67 | ????0.012 | ????99.91 |
| ??P110 | ????12.24 | ????0.008 | ????99.93 | |
| ??C90 | ????57.15 | ????0.025 | ????99.96 | |
| ????90 | ??N80 | ????22.60 | ????0.11 | ????99.5 |
| ??P110 | ????19.15 | ????0.114 | ????99.4 | |
| ??C90 | ????18.65 | ????0.137 | ????99.3 | |
| ????110 | ??N80 | ????22.70 | ????0.285 | ????98.7 |
| ??P110 | ????15.70 | ????0.321 | ????98.0 | |
| ??C90 | ????9.05 | ????0.426 | ????95.3 | |
In a word, corrosion inhibitor product of the present invention is that a kind of oil is molten, the chemical of water dispersible, it in the metallic surface with the double colloidal layers mode film forming of uniqueness, the mixing and absorption feature that is " alternate type " and " interface type ", characteristics such as this inhibiter has easy absorption, one-tenth thickness, the adsorption film life-span is long, consumption is few, can not damage, easily be accepted by the oil field field staff to human body.In the Oil extraction process, to containing CO
2Oil well in inject this inhibiter, not only can control CO effectively
2To the corrosion of tubing and casing, and can significantly reduce remedial operation, reduce production costs.
Claims (8)
1. oil field novel anti CO
2Corrosion inhibitor, this inhibiter comprises: (A) 25-40% (weight) tetrahydroglyoxaline contains sulfur derivatives, (B) 20-30% (weight) alkyl phosphate, (C) 5-15% (weight) alkynol, (D) 10-20% (weight) nonionogenic tenside reaches (E) 20-30% (weight) solvent.Wherein,
The general structure that tetrahydroglyoxaline contains sulfur derivatives is:
In the formula: R
1Be C
12-C
20Alkyl or alkenyl; R
2, R
3Be C
0-C
5Alkyl or alkenyl.The general structure of alkyl phosphate is:
In the formula: R
4Be C
8-C
14Alkyl; R
5=R
4Or H; R
6=R
4Or H;
Alkynol is C
3-C
6Alcohol;
Nonionogenic tenside is aliphatic alcohol polyethenoxy base ether or alkylphenol-polyethenoxy base ether;
Solvent is ethanol, Virahol or ethylene glycol.
2. inhibiter according to claim 1, it is synthetic by following method that wherein said tetrahydroglyoxaline contains sulfur derivatives: with lipid acid, part polyamines and take water solvent join simultaneously have stir and the reactor of water distilling apparatus in, after 3 hours, in reactor, drip another part polyamines in reaction under 145 ℃～175 ℃ again; Continue to heat up, reacted 2-5 hour down in 240 ℃～260 ℃, obtain the tetrahydroglyoxaline intermediate, this moment, the acid number of reaction product was lower than 2.0mgKOH/g; Be cooled to below 100 ℃, again to wherein adding substituting group thiocarbamide and alkyl alcohol, 130 ℃～155 ℃ condensation reaction 4-6 hour, obtain tetrahydroglyoxaline after the cooling and contain sulfur derivatives.
3. inhibiter according to claim 2, the acid number of wherein said tetrahydroglyoxaline intermediate should be lower than 2.0mgKOH/g.
4. inhibiter according to claim 1, wherein said alkyl phosphate is synthetic by following method: with alkyl alcohol and P
2O
5Join respectively in the reactor that has agitator and thermometer, under agitation slowly heat up, react 3-5 hour postcooling down in 40 ℃～70 ℃ and obtain the mixed alkyl phosphoric acid ester.
5. inhibiter according to claim 1, wherein said alkynol are propiolic alcohol.
6. inhibiter according to claim 1, wherein said nonionogenic tenside are aliphatic alcohol polyethenoxy (20) ether or octyl phenol polyoxy ethene (10) ether.
7. inhibiter according to claim 1, wherein said solvent are Virahol.
8. the method for preparing the described inhibiter of claim 1, this method comprises the steps:
With lipid acid, part polyamines and take water solvent join simultaneously have stir and the reactor of water distilling apparatus in, reaction is after 3 hours down at 145 ℃～175 ℃, and dropping another part polyamines continues to heat up, reacted 2-5 hour down in 240 ℃～260 ℃, obtain the tetrahydroglyoxaline intermediate;
Temperature of reaction is reduced to below 100 ℃, again to wherein adding substituting group thiocarbamide and alkanol, 130 ℃～155 ℃ condensation reaction 4-6 hour, obtain tetrahydroglyoxaline after the cooling and contain sulfur derivatives;
With alkyl alcohol and P
2O
5Join respectively in the reactor that has agitator and thermometer, under agitation slowly heat up, react 3-5 hour postcooling down in 40 ℃～70 ℃ and obtain the mixed alkyl phosphoric acid ester;
Above-mentioned tetrahydroglyoxaline is contained sulfur derivatives, alkyl phosphate and alkynol, nonionogenic tenside and solvent according to the described mixed of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001096877A CN1144856C (en) | 2000-06-21 | 2000-06-21 | Corrosion inhibitor resisting CO2 corrosion for oil field |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001096877A CN1144856C (en) | 2000-06-21 | 2000-06-21 | Corrosion inhibitor resisting CO2 corrosion for oil field |
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| Publication Number | Publication Date |
|---|---|
| CN1277240A true CN1277240A (en) | 2000-12-20 |
| CN1144856C CN1144856C (en) | 2004-04-07 |
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|---|---|---|---|
| CNB001096877A Expired - Fee Related CN1144856C (en) | 2000-06-21 | 2000-06-21 | Corrosion inhibitor resisting CO2 corrosion for oil field |
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|---|---|---|---|---|
| WO2007112620A1 (en) * | 2006-04-04 | 2007-10-11 | Petrochina Company Limited | An inhibitor of inhibiting metal corrosion and the preparing method of it |
| CN100453704C (en) * | 2003-09-08 | 2009-01-21 | 成都孚吉科技有限责任公司 | Solid inhibitor and preparation method thereof |
| CN100453703C (en) * | 2005-02-07 | 2009-01-21 | 长江大学 | Inhibitor for controlling carbon dioxide corrosion and production thereof |
| CN100591803C (en) * | 2006-09-04 | 2010-02-24 | 中国石油集团川庆钻探工程有限公司 | anti-H2S and CO2Corrosion inhibitor under combined action |
| CN102234502A (en) * | 2010-04-21 | 2011-11-09 | 华中科技大学 | Corrosion inhibitor and preparation method |
| CN102268677A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Corrosion inhibitor for inhibiting H2S/CO2 corrosion and preparation method thereof |
| CN102392264A (en) * | 2011-11-23 | 2012-03-28 | 上海申和热磁电子有限公司 | Corrosion inhibitor, cleaning solution and application thereof |
| CN102747374A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method and application |
| CN102746839A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method |
| CN103114290A (en) * | 2013-02-04 | 2013-05-22 | 胜利油田胜利勘察设计研究院有限公司 | Sulfur element containing bicycloimidazoline derivant corrosion inhibitor |
| 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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2000
- 2000-06-21 CN CNB001096877A patent/CN1144856C/en not_active Expired - Fee Related
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| CN100453704C (en) * | 2003-09-08 | 2009-01-21 | 成都孚吉科技有限责任公司 | Solid inhibitor and preparation method thereof |
| CN100453703C (en) * | 2005-02-07 | 2009-01-21 | 长江大学 | Inhibitor for controlling carbon dioxide corrosion and production thereof |
| WO2007112620A1 (en) * | 2006-04-04 | 2007-10-11 | Petrochina Company Limited | An inhibitor of inhibiting metal corrosion and the preparing method of it |
| CN100526508C (en) * | 2006-04-04 | 2009-08-12 | 中国石油天然气股份有限公司 | Corrosion inhibitor for inhibiting metal corrosion and preparation method thereof |
| CN100591803C (en) * | 2006-09-04 | 2010-02-24 | 中国石油集团川庆钻探工程有限公司 | anti-H2S and CO2Corrosion inhibitor under combined action |
| CN102234502B (en) * | 2010-04-21 | 2013-03-27 | 华中科技大学 | Corrosion inhibitor and preparation method |
| CN102234502A (en) * | 2010-04-21 | 2011-11-09 | 华中科技大学 | Corrosion inhibitor and preparation method |
| CN102268677A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Corrosion inhibitor for inhibiting H2S/CO2 corrosion and preparation method thereof |
| CN102747374B (en) * | 2011-04-22 | 2014-04-09 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method and application |
| CN102746839A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method |
| CN102747374A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method and application |
| CN102746839B (en) * | 2011-04-22 | 2014-06-18 | 中国石油化工股份有限公司 | Oil-soluble corrosion inhibitor, its preparation method |
| CN102392264A (en) * | 2011-11-23 | 2012-03-28 | 上海申和热磁电子有限公司 | Corrosion inhibitor, cleaning solution and application thereof |
| CN102392264B (en) * | 2011-11-23 | 2016-06-15 | 上海申和热磁电子有限公司 | A kind of inhibiter, scavenging solution and application thereof |
| CN103114290A (en) * | 2013-02-04 | 2013-05-22 | 胜利油田胜利勘察设计研究院有限公司 | Sulfur element containing bicycloimidazoline derivant corrosion inhibitor |
| 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 |
| CN106285566A (en) * | 2016-08-01 | 2017-01-04 | 中嵘能源科技集团有限公司 | A kind of air injection anticorrosion completion method and the inhibition acid solution wherein used |
| CN110777383A (en) * | 2019-01-08 | 2020-02-11 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant carbon dioxide corrosion-resistant corrosion inhibitor and preparation method thereof |
| CN110777383B (en) * | 2019-01-08 | 2021-09-28 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant carbon dioxide corrosion-resistant corrosion inhibitor and preparation method thereof |
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