CN102260873A - Method for enhancing use effect of high-temperature corrosion inhibitor of oil-refining device - Google Patents
Method for enhancing use effect of high-temperature corrosion inhibitor of oil-refining device Download PDFInfo
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- CN102260873A CN102260873A CN2010101843196A CN201010184319A CN102260873A CN 102260873 A CN102260873 A CN 102260873A CN 2010101843196 A CN2010101843196 A CN 2010101843196A CN 201010184319 A CN201010184319 A CN 201010184319A CN 102260873 A CN102260873 A CN 102260873A
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- naphthenic acid
- alkali metal
- metal salt
- corrosion inhibitor
- oil
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Abstract
The invention relates to a method for enhancing a use effect of a high-temperature corrosion inhibitor of an oil-refining device, wherein a naphthenic acid alkali metal salt is added in a material flow of the oil-refining device so as to enable the naphthenic acid alkali metal salt and the high-temperature corrosion inhibitor to be in contact with corroding parts of the oil-refining device. According to the invention, the naphthenic acid alkali metal salt which is added is beneficial to forming of a complete and compact protecting membrane of the corrosion inhibitor on the metallic surface, thus the use effect of the corrosion inhibitor is enhanced.
Description
Technical field
The present invention relates to a kind of method that improves the high temperature inhibitor for oil refining apparatus result of use.
Background technology
In recent years, whole world heavy, crude oil with poor quality output increase sharply, account for the global crude oil ratio and rise year by year, but limited by the oil refining apparatus processing condition, demand growth is slow, therefore the price poor quality widens gradually, therefore, processing highly acid crude oil has certain cost advantage under soaring oil prices, but processes when containing acid or high-acid crude oil, one of the most scabrous problem is the corrosion of naphthenic acid to processing unit (plant), and etching problem directly has influence on the safe operation of production.
Naphthenic acid corrosion mainly occurs in normal, the vacuum still of oil refining apparatus, and corrosion-prone position often comprises, transfer line etc. at the bottom of vacuum still tower body, filler, feed zone, side line and the tower.At present, the method that solves naphthenic acid corrosion can be divided into three kinds: (1) refining equipment, device are used corrosion-resistant material instead, the material upgrading.(2) control processing flow velocity, flow state are optimized design to the refining equipment structure.(3) improve the refining process process, as crude oil mixing, crude oil deacidification, to perishable position filling inhibiter etc.At present, crude oil mixing is the most a kind of method of extensive employing of domestic refining high-acid crude oil, is about to contain acid or high-acid crude oil and low sour crude oil mixes, and the commingled crude acid number is lower than below the threshold value 0.5mgKOH/g that naphthenic acid corrosion takes place.In addition; adding inhibiter is the most simple scheme that solves high temperature corrosion in the high-acid crude oil course of processing, and each processes the refinery of acid-containing raw oil, is all adding inhibiter basically; make it can either handle crude oil with high acid value, can directly protect again corrosion location.
The inhibiter that is used to suppress naphthenic acid corrosion also claims high-temperature corrosion inhibitor; be some compounds that contain groups such as S, P, N, O; these compounds form one deck compact protective film by the mode and the melts combine of physical adsorption or chemical reaction; corrosive medium and metal are kept apart, take place thereby suppress corrosive.But in the process that high-temperature corrosion inhibitor uses, find: owing to exist corrosion product in the metallic surface; the protective membrane that makes inhibiter be difficult to touch the metallic surface or form in the metallic surface is compact and complete inadequately, thereby causes the reduction even the failure of inhibiter result of use.
Summary of the invention
The invention provides a kind of method that improves the high temperature inhibitor for oil refining apparatus result of use, this method can strengthen the result of use of high-temperature corrosion inhibitor, thereby more effectively suppresses the corrosion of naphthenic acid to oil refining apparatus.
A kind of method that improves the high temperature inhibitor for oil refining apparatus result of use joins an alkali metal salt of naphthenic acid in the streams of oil refining apparatus, and an alkali metal salt of naphthenic acid is contacted with the corrosion location of oil refining apparatus with high-temperature corrosion inhibitor.
The present invention has no particular limits the implantation site that adds of an alkali metal salt of naphthenic acid, the an alkali metal salt that both can add naphthenic acid in the charging of oil refining apparatus in advance also can be at an alkali metal salt of the adding of the position before perishable position of oil refining apparatus or oil refining apparatus corrosion location naphthenic acid; Both can after high-temperature corrosion inhibitor mixes, add in the streams of oil refining apparatus, also can add respectively in the streams of oil refining apparatus with high-temperature corrosion inhibitor; Both can add, also can add in the stationary phase of using high-temperature corrosion inhibitor at the initial stage of using high-temperature corrosion inhibitor; Both can add oil refining apparatus, also can add oil refining apparatus, contact for some time with high-temperature corrosion inhibitor jointly with the corrosion location of oil refining apparatus as long as can satisfy an alkali metal salt that makes naphthenic acid from a plurality of positions from a position.
Under the preferred situation, an alkali metal salt of naphthenic acid is dissolved in solvent after, join again in the streams of oil refining apparatus.The effect of solvent is to make the dissolving of an alkali metal salt of naphthenic acid, is convenient to join in the oil refining apparatus, and those skilled in the art can be according to instruction of the present invention, in conjunction with the basic general knowledge of this area, the kind of selective solvent and consumption voluntarily.
Under another preferred situation, an alkali metal salt of naphthenic acid with after high-temperature corrosion inhibitor mixes, is joined in the streams of oily device.
With the every gram material in the oil refining apparatus streams is benchmark, and an alkali metal salt add-on of naphthenic acid is preferably 10 μ g~10000 μ g, more preferably 50 μ g~5000 μ g.
The joining day of an alkali metal salt of naphthenic acid is preferably 0.5h~48h, more preferably 1h~12h.
The method that is prepared the naphthenic acid an alkali metal salt by naphthenic acid belongs to prior art, and the present invention repeats no more.Basic general knowledge as this area, naphthenic acid be mainly derived from oil, the naphthenic acid of being separated by refining of petroleum products is a mixture, the present invention preferably adopts this naphthenic acid an alkali metal salt by hybrid ring alkanoic acid preparation, but the present invention does not get rid of the naphthenic acid an alkali metal salt that adopts the single naphthenic acid preparation of purifying or obtain by organic synthesis yet.The present invention also has no particular limits the carbon number of naphthenic acid, as long as can be dissolved in the streams that is added.
The present invention has no particular limits inhibiter.
Those skilled in the art know how to use inhibiter.Generally speaking, be benchmark with the every gram material in the streams, the consumption of high-temperature corrosion inhibitor is 5~200 μ g, preferred 10~100 μ g; Temperature range is 150~600 ℃, preferred 210~350 ℃.At the use initial stage, the consumption of high-temperature corrosion inhibitor is higher; In stationary phase, the consumption of high-temperature corrosion inhibitor is lower.
Discover naphthenic acid corrosion is sex by naphthenate: an alkali metal salt of naphthenic acid is a kind of corrosion product clean-out system; effect with stripping metal surface corrosion product; more help inhibiter by an alkali metal salt that will add naphthenic acid and form complete, compact protective film in the metallic surface, thus the result of use of raising inhibiter.Adopt method of the present invention to need not extra procuring equipment, the cleaning of metallic surface and the film forming of inhibiter are finished simultaneously.
Embodiment
Embodiment 1:
Corrosion test is carried out in the 500mL autoclave.
Test piece material: 20# carbon steel.Test temperature: 270~280 ℃.
The acid-containing raw oil of corrosive medium: TAN=3.47mgOH/g, inhibiter (dimethylphosphite) add-on 100 μ g/g, sodium napthionate (naphthenic acid by weight-average molecular weight 300 makes, naphthenic acid carbon number 16~30) add-on 1000 μ g/g, scavenging period 2h.Test-results shows that the test piece surface that adds sodium napthionate forms even protective membrane, and erosion rate is 0.01mm/a.
Adopt identical test conditions, just do not add sodium napthionate, compare test.Test-results shows that the surperficial protective membrane that forms of test piece that does not add sodium napthionate is inhomogeneous, and erosion rate is 0.17mm/a,
Embodiment 2:
Corrosion test is carried out in the 500mL autoclave.
Test piece material: 20# carbon steel.Test temperature: 300~310 ℃.
Corrosive medium: TAN=1.68mgOH/g contains acid fraction oil, 350 ℃~420 ℃ of distillate boiling ranges, inhibiter (dimethylphosphite) add-on 50 μ g/g, (naphthenic acid by weight-average molecular weight 300 makes cyclic potassium naphthenate, naphthenic acid carbon number 16~30) add-on 300 μ g/g, scavenging period 1h.Test-results shows that the test piece surface that adds cyclic potassium naphthenate forms even protective membrane, and erosion rate is 0.1mm/a.
Adopt identical test conditions, just do not add cyclic potassium naphthenate, compare test.Test-results shows that the test piece surface that does not add cyclic potassium naphthenate does not form protective membrane, and erosion rate is 1.2mm/a.
Claims (9)
1. a method that improves the high temperature inhibitor for oil refining apparatus result of use is characterized in that, an alkali metal salt of naphthenic acid is joined in the streams of oil refining apparatus, and an alkali metal salt of naphthenic acid is contacted with the corrosion location of oil refining apparatus with high-temperature corrosion inhibitor.
2. according to the method for claim 1, it is characterized in that, is benchmark with the every gram material in the oil refining apparatus streams, and an alkali metal salt add-on of naphthenic acid is 10 μ g~10000 μ g.
3. according to the method for claim 2, it is characterized in that, is benchmark with the every gram material in the oil refining apparatus streams, and an alkali metal salt add-on of naphthenic acid is 50 μ g~5000 μ g.
4. according to the method for claim 1, it is characterized in that the joining day of an alkali metal salt of naphthenic acid is 0.5h~48h.
5. according to the method for claim 4, it is characterized in that the joining day of an alkali metal salt of naphthenic acid is 1.0h~12h.
6. according to the method for claim 1, it is characterized in that when an alkali metal salt of naphthenic acid contacted with the corrosion location of oil refining apparatus with high-temperature corrosion inhibitor, temperature was 150~600 ℃.
7. according to the method for claim 6, it is characterized in that when an alkali metal salt of naphthenic acid contacted with the corrosion location of oil refining apparatus with high-temperature corrosion inhibitor, temperature was 210~350 ℃.
8. according to the method for claim 1, it is characterized in that, an alkali metal salt of naphthenic acid is dissolved in solvent after, join again in the streams of oil refining apparatus.
9. according to the method for claim 1, it is characterized in that, an alkali metal salt of naphthenic acid with after high-temperature corrosion inhibitor mixes, is joined in the streams of oil refining apparatus.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103952690A (en) * | 2014-03-23 | 2014-07-30 | 烟台恒迪克能源科技有限公司 | Water-soluble powdery metal antirust agent composition |
WO2021199439A1 (en) * | 2020-04-03 | 2021-10-07 | 株式会社片山化学工業研究所 | Method for preventing heat exchanger fouling in oil process |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1894389A (en) * | 2003-10-17 | 2007-01-10 | 弗劳尔科技公司 | Compositions, configurations, and methods of reducing naphthenic acid corrosivity |
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Patent Citations (1)
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CN1894389A (en) * | 2003-10-17 | 2007-01-10 | 弗劳尔科技公司 | Compositions, configurations, and methods of reducing naphthenic acid corrosivity |
Non-Patent Citations (4)
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103952690A (en) * | 2014-03-23 | 2014-07-30 | 烟台恒迪克能源科技有限公司 | Water-soluble powdery metal antirust agent composition |
WO2021199439A1 (en) * | 2020-04-03 | 2021-10-07 | 株式会社片山化学工業研究所 | Method for preventing heat exchanger fouling in oil process |
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