CN102260873B - 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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- CN102260873B CN102260873B CN 201010184319 CN201010184319A CN102260873B CN 102260873 B CN102260873 B CN 102260873B CN 201010184319 CN201010184319 CN 201010184319 CN 201010184319 A CN201010184319 A CN 201010184319A CN 102260873 B CN102260873 B CN 102260873B
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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, have certain cost advantage at Processing HA Oil under High Oil Price, but when processing contains acid or high-acid crude oil, one of the most scabrous problem be naphthenic acid to the corrosion of 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 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) controlled working 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, the inhibiter etc. of annotating to perishable position.At present, crude oil mixing is a kind of method that domestic refining high-acid crude oil the most extensively adopts, and is about to contain acid or high-acid crude oil and low sour crude oil mixing, makes below the threshold value 0.5mgKOH/g of commingled crude acid number lower than the naphthenic acid corrosion generation.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 basically all adding inhibiter; make it can either process crude oil with high acid value, can directly protect corrosion location again.
The inhibiter that is used for the inhibition naphthenic acid corrosion also claims high-temperature corrosion inhibitor; some compounds that contain the groups such as S, P, N, O; these compounds are by the mode of physical adsorption or chemical reaction and the protective membrane of melts combine formation one deck densification; corrosive medium and metal are kept apart, thus the generation of inhibition corrosion.But find in the process that high-temperature corrosion inhibitor uses: owing to existing 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 not, thereby causes the reduction of inhibiter result of use even failed.
Summary of the invention
The invention provides a kind of method that improves the high temperature inhibitor for oil refining apparatus result of use, the method can strengthen the result of use of high-temperature corrosion inhibitor, thereby more effectively suppresses naphthenic acid to the corrosion of 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, both can add in advance an alkali metal salt of naphthenic acid in the charging of oil refining apparatus, also can the position before the perishable position of oil refining apparatus or oil refining apparatus corrosion location add an alkali metal salt of naphthenic acid; Both can with after high-temperature corrosion inhibitor mixes together with 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 at the initial stage of using high-temperature corrosion inhibitor, also can add in the stationary phase of using high-temperature corrosion inhibitor; Both can add oil refining apparatus from a position, also can add oil refining apparatus from a plurality of positions, jointly contact for some time with high-temperature corrosion inhibitor with the corrosion location of oil refining apparatus as long as can satisfy an alkali metal salt that makes naphthenic acid.
In preferred situation, after an alkali metal salt of naphthenic acid is dissolved in solvent, then join 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 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.
In 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.
Every gram material in the oil refining apparatus streams is as 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 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 adds.
The present invention has no particular limits inhibiter.
Those skilled in the art know how to use inhibiter.Generally, the every gram material in the streams is as benchmark, and 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.
By naphthenate, the research of causticity of naphthenic acids impact is found: an alkali metal salt of naphthenic acid is a kind of corrosion product clean-out system; effect with stripping metal surface corrosion product; more be conducive to inhibiter by an alkali metal salt that will add naphthenic acid and form complete, fine and close protective membrane 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 completed 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, adds the even protective membrane of test piece surface formation of sodium napthionate, and erosion rate is 0.01mm/a.
Adopt identical test conditions, just do not add sodium napthionate, compare test.Test-results shows, do not add the protective membrane that the test piece surface of sodium napthionate forms 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, adds the even protective membrane of test piece surface formation of cyclic potassium naphthenate, and erosion rate is 0.1mm/a.
Adopt identical test conditions, just do not add cyclic potassium naphthenate, compare test.Test-results shows, do not add the test piece surface of cyclic potassium naphthenate 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, the every gram material in the oil refining apparatus streams is as benchmark, 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, the every gram material in the oil refining apparatus streams is as benchmark, 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, after an alkali metal salt of naphthenic acid is dissolved in solvent, then join 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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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010184319 CN102260873B (en) | 2010-05-27 | 2010-05-27 | Method for enhancing use effect of high-temperature corrosion inhibitor of oil-refining device |
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| CN 201010184319 CN102260873B (en) | 2010-05-27 | 2010-05-27 | Method for enhancing use effect of high-temperature corrosion inhibitor of oil-refining device |
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| CN102260873B true CN102260873B (en) | 2013-06-05 |
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| CN103952690B (en) * | 2014-03-23 | 2018-03-09 | 汕头市联达包装材料有限公司 | A kind of water-soluble powder metal antirust agent composition |
| JP7537685B2 (en) | 2020-04-03 | 2024-08-21 | 株式会社片山化学工業研究所 | How to prevent fouling of heat exchangers in petroleum processes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| "常减压装置环烷酸腐蚀与防护";苏金华;《石油和化工设备》;20051231(第6期);第29-30页 * |
| "缓蚀剂的分类和发展方向";王英等;《全面腐蚀控制》;20090228;第23卷(第2期);第25页 * |
| 王英等."缓蚀剂的分类和发展方向".《全面腐蚀控制》.2009,第23卷(第2期),第25页. |
| 苏金华."常减压装置环烷酸腐蚀与防护".《石油和化工设备》.2005,(第6期),第29-30页. |
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