CN102994149B - Corrosion-retarding agent and preparation method thereof, and method for reducing acid-containing hydrocarbon oil corrosivity - Google Patents
Corrosion-retarding agent and preparation method thereof, and method for reducing acid-containing hydrocarbon oil corrosivity Download PDFInfo
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- CN102994149B CN102994149B CN201110265061.7A CN201110265061A CN102994149B CN 102994149 B CN102994149 B CN 102994149B CN 201110265061 A CN201110265061 A CN 201110265061A CN 102994149 B CN102994149 B CN 102994149B
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Abstract
The invention relates to a corrosion-retarding agent and a preparation method thereof, and a method for reducing acid-containing hydrocarbon oil corrosivity. The corrosion-retarding agent comprises 50-99.5% of hydrocarbon oil by mass and 0.5-50 % of petroleum acid iron. With the corrosion-retarding agent and the acid-containing hydrocarbon oil corrosivity reducing method provided by the invention, corrosion of acid-containing hydrocarbon oil upon positions such as atmospheric and vacuum tower body, filling material and side lines can be effectively inhibited.
Description
Technical field
The present invention relates to a kind of inhibiter and preparation method thereof and the corrosive method of reduction acid-containing hydrocarbon oil.
Background technology
In recent years, whole world heavy, crude oil with poor quality output increase sharply, account for global crude oil ratio to rise year by year, but by the restriction of oil refining apparatus processing condition, demand growth is slow, causes price poor quality to widen gradually, therefore at Processing HA Oil under High Oil Price, there is certain cost advantage, but when processing is 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.At present, the method solving naphthenic acid corrosion can be divided into three kinds: (1) refining equipment, device use corrosion-resistant material instead, and material upgrades.(2) controlled working flow velocity, flow state, is optimized design to refining equipment structure.(3) improve refining process process, as crude oil mixing, crude oil deacidification, to perishable position filling inhibiter etc.Adding inhibiter is the most simple scheme solving high temperature corrosion in the high-acid crude oil course of processing, and the refinery of each processing acid-containing raw oil, is substantially all adding inhibiter, making it process crude oil with high acid value, can directly protect corrosion location again.
Application inhibiter suppresses the research of naphthenic acid corrosion to have the history of nearly 50 years, main based on amine and acid amides in early days, but this kind of inhibiter at high temperature easily decomposes, therefore gradually replace by other medicament.
Petrolite company has applied for phosphorous acid two (three) alkyl ester and thiazoline (2 in nineteen ninety, 2-pentylidene-4,5-tetramethylene-1,3-thiazoles quinoline) compound is for suppressing the patent (patent No. US4941994) of naphthenic acid high temperature corrosion.
Exxon company has applied for that in 1993 organic polysulfide is for suppressing the patent (patent No. US5182013) of naphthenic acid high temperature corrosion.
The patent US5252254 of Nalco company reports the restraining effect of sulfonated alkylphenol to naphthenic acid high temperature corrosion.
Betz laboratory reports the restraining effect of mercapto-triazine compound to naphthenic acid high temperature corrosion at the patent US5464525 that nineteen ninety-five applies for.
Luoyang Petrochemical engineering corporation of China Petrochemical Industry reports the effect of alkyl phosphate and alkyl diazine ring system compounds compound copolymer suppression naphthenic acid corrosion at the patent CN1035020 of application in 1997.
Exxon-Mobil research and engineering corporation report the restraining effect of 4-sulfosalicylic phthalate to naphthenic acid high temperature corrosion at the patent US6583091 of application in 2003, US6537950 reports the restraining effect of triphenyl-stibine to naphthenic acid high temperature corrosion, US6559104 reports three acidic functionality substituted benzenes to the restraining effect of naphthenic acid high temperature corrosion, compound has 5-hydroxy-phthalate, 1,2,3-tri-phenylformic acid, 1,3,5-tri-phenylformic acid.NALCO company commercial N-5180 inhibiter is the compound (alkyl phosphate, alkyl sulfuric ester, alkyl imidazoline) of phosphoric acid ester-amine.
CN1894389A describes a kind of method alleviating naphthenic acid corrosion, will can alleviate the corrosion of naphthenic acid containing weak erosive β acid fraction oil and severe corrosive α acid fraction oil mixed refining.
Summary of the invention
The invention provides a kind of inhibiter and preparation method thereof and the corrosive method of reduction acid-containing hydrocarbon oil, adopt this inhibiter and reduce the naphthenic acid corrosion that the corrosive method of acid-containing hydrocarbon oil effectively can reduce acid-containing hydrocarbon oil.
A kind of inhibiter, the petroleum acid iron of the hydrocarbon ils containing 50 quality % ~ 99.5 quality % and 0.5 quality % ~ 50 quality %.
In described inhibiter, the content of hydrocarbon ils is preferably 60 quality % ~ 95 quality %.
In described inhibiter, the content of petroleum acid iron is preferably 5 quality % ~ 40 quality %.
The present invention has no particular limits hydrocarbon ils, as long as can dissolve petroleum acid iron, and has certain mobility, is convenient to be joined in acid-containing hydrocarbon oil.
Inhibiter of the present invention can also contain existing inhibition component.
A preparation method for inhibiter, comprising:
(1) petroleum acid and alkali metal hydroxide are reacted, obtain petroleum acid an alkali metal salt;
(2) in water, petroleum acid an alkali metal salt and iron(ic) chloride or iron protochloride are reacted, separate out throw out;
(3) use petroleum ether dissolution throw out, after aqueous ethanolic solution washing, steam sherwood oil, obtain petroleum acid iron;
(4) petroleum acid iron is mixed with hydrocarbon ils, obtain product.
The acid number of described petroleum acid is preferably 100 ~ 270mgKOH/g.Described petroleum acid both by commercially available, also can be prepared by prior art.
Specifically, aforesaid method can carry out according to the following steps.
Under stirring, petroleum acid is warming up to 70 ~ 95 DEG C, adds alkali metal hydroxide aqueous solution, be 9 ~ 10 to pH value, obtain petroleum acid aqueous solution of alkali metal salt, then iron(ic) chloride or ferrous chloride aqueous solution are joined in petroleum acid aqueous solution of alkali metal salt, when pH value of solution is 2 ~ 3, petroleum acid iron is separated out, with sherwood oil by it dissolving, after aqueous ethanolic solution washing, steam sherwood oil, obtain petroleum acid iron, petroleum acid iron is mixed with hydrocarbon ils, obtains corrosion inhibitor product.
A kind of corrosive method of reduction acid-containing hydrocarbon oil, comprising: join in acid-containing hydrocarbon oil by petroleum acid iron, relative to the quality of acid-containing hydrocarbon oil, the consumption of petroleum acid iron is 5 ~ 20000mg/kg, the acid number >=0.5mgKOH/g of described acid-containing hydrocarbon oil.
The acid number (TAN) of described acid-containing hydrocarbon oil preferably >=2.0mgKOH/g.
Relative to the quality of acid-containing hydrocarbon oil, the consumption of petroleum acid iron is preferably 10 ~ 5000mg/kg.
The true boiling point of described acid-containing hydrocarbon oil preferably≤530 DEG C, more preferably between 180 DEG C ~ 530 DEG C.
In preferred situation, first by petroleum acid dissolved ferric iron in hydrocarbon ils, be then injected into acid-containing hydrocarbon oil from the perishable position of pipeline, storage tank, equipment or device.
When adding petroleum acid iron, the temperature of acid-containing hydrocarbon oil can be 100 ~ 600 DEG C, is preferably 180 ~ 350 DEG C.
Adopting inhibiter of the present invention and lowering the corrosive method of acid-containing hydrocarbon oil effectively to suppress acid-containing hydrocarbon oil to the corrosion at the positions such as ordinary decompression column tower body, filler and side line, and the present invention is equally applicable to the protection against corrosion of the hardware of other conditions of similarities.
Embodiment
Petroleum acid iron synthesizer comprises 500mL there-necked flask, stirring motor, reflux condensing tube, thermometer and electric heating cover.Corrosion test is carried out in 500mL autoclave, and characterize corrosion mitigating effect with metal weight loss, test piece material is 20# carbon steel.All concentration in embodiment are mass percentage concentration.
Embodiment 1
Band stirs in there-necked flask and adds petroleum acid A (acid number 220mgKOH/g) 20g, stirring is warmed up to 70 ~ 90 DEG C, drips the aqueous sodium hydroxide solution of 2%, reaches 9 ~ 10 to pH value, obtain the petroleum acid sodium aqueous solution, again the ferric chloride in aqueous solution of 5% being dropped to petroleum acid receives in the aqueous solution, and when pH value of solution is 2 ~ 3, reaction product petroleum acid iron is separated out, with petroleum ether dissolution, aqueous ethanolic solution washs, and steams sherwood oil, obtains petroleum acid iron A.
Embodiment 2
Band stirs in there-necked flask and adds petroleum acid B (acid number 120mgKOH/g) 20g, stirring is warmed up to 85 ~ 95 DEG C, drips the potassium hydroxide aqueous solution of 2%, reaches 9 ~ 10 to pH value, obtain petroleum acid aqueous solutions of potassium, drop in petroleum acid aqueous solutions of potassium by the ferrous chloride aqueous solution of 5% again, when pH value of solution is 2 ~ 3, reaction product petroleum acid iron is separated out, with petroleum ether dissolution, aqueous ethanolic solution washs, and steams sherwood oil, obtains petroleum acid iron B.
Embodiment 3
Test temperature is 230 DEG C, and test period is 2h.Corrosive medium is the acid-containing raw oil of TAN=1.47mgOH/g, gets 270 ~ 350 DEG C of cuts respectively and 350 ~ 530 DEG C of cuts carry out corrosion test.Adopt petroleum acid iron A as inhibition component, test-results is in table 1.
Table 1
Embodiment 4
Test temperature is 270 DEG C; Test period is 2h.Corrosive medium is the high-acid crude oil of TAN=6.24mgOH/g, gets 270 ~ 350 DEG C of cuts respectively and 350 ~ 530 DEG C of cuts carry out corrosion test.Adopt petroleum acid iron B as inhibition component, test-results is in table 2.
Table 2
Claims (13)
1. reduce an inhibiter for acid-containing hydrocarbon oil naphthenic acid corrosion, the petroleum acid iron of the hydrocarbon ils containing 50 quality % ~ 99.5 quality % and 0.5 quality % ~ 50 quality %.
2. according to inhibiter according to claim 1, its characteristic is, the content of hydrocarbon ils is 60 quality % ~ 95 quality %.
3. according to inhibiter according to claim 1, its characteristic is, the content of petroleum acid iron is 5 quality % ~ 40 quality %.
4. the preparation method of inhibiter according to claim 1, comprising:
(1) petroleum acid and alkali metal hydroxide are reacted, obtain petroleum acid an alkali metal salt;
(2) in water, petroleum acid an alkali metal salt and iron(ic) chloride or iron protochloride are reacted, separate out throw out;
(3) use petroleum ether dissolution throw out, after aqueous ethanolic solution washing, steam sherwood oil, obtain petroleum acid iron;
(4) petroleum acid iron is mixed with hydrocarbon ils, obtain product.
5. in accordance with the method for claim 4, it is characterized in that, the acid number of described petroleum acid is 100 ~ 270mgKOH/g.
6. reduce a method for acid-containing hydrocarbon oil causticity of naphthenic acids, comprising: join in acid-containing hydrocarbon oil by petroleum acid iron, relative to the quality of acid-containing hydrocarbon oil, the consumption of petroleum acid iron is 5 ~ 20000mg/kg, the acid number >=0.5mgKOH/g of described acid-containing hydrocarbon oil.
7. in accordance with the method for claim 6, it is characterized in that, the acid number >=2.0mgKOH/g of described acid-containing hydrocarbon oil.
8. in accordance with the method for claim 6, it is characterized in that, relative to the quality of acid-containing hydrocarbon oil, the consumption of petroleum acid iron is 10 ~ 5000mg/kg.
9. in accordance with the method for claim 6, it is characterized in that, true boiling point≤530 DEG C of described acid-containing hydrocarbon oil.
10. in accordance with the method for claim 9, it is characterized in that, the true boiling point of described acid-containing hydrocarbon oil is between 180 DEG C ~ 530 DEG C.
11. in accordance with the method for claim 6, it is characterized in that, first by petroleum acid dissolved ferric iron in hydrocarbon ils, be then injected into acid-containing hydrocarbon oil from the perishable position of pipeline, storage tank, equipment or device.
12., according to the method described in claim 6 or 11, is characterized in that, when adding petroleum acid iron, the temperature of acid-containing hydrocarbon oil is 100 ~ 600 DEG C.
13. in accordance with the method for claim 12, it is characterized in that, when adding petroleum acid iron, the temperature of acid-containing hydrocarbon oil is 180 ~ 350 DEG C.
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Citations (4)
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|---|---|---|---|---|
| CN1163301A (en) * | 1996-04-24 | 1997-10-29 | 胜利石油管理局勘察设计研究院 | Acidifying corrosion inhibitor for oil well and its preparation |
| CN1193990A (en) * | 1995-08-25 | 1998-09-23 | 埃克森研究工程公司 | Process for decreasing the acid content and corrosivity of crudes |
| CN1894389A (en) * | 2003-10-17 | 2007-01-10 | 弗劳尔科技公司 | Compositions, configurations, and methods of reducing naphthenic acid corrosivity |
| CN101875857A (en) * | 2009-04-30 | 2010-11-03 | 中国石油化工股份有限公司 | Method for reducing corrosivity of acidiferous distillate oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193990A (en) * | 1995-08-25 | 1998-09-23 | 埃克森研究工程公司 | Process for decreasing the acid content and corrosivity of crudes |
| CN1163301A (en) * | 1996-04-24 | 1997-10-29 | 胜利石油管理局勘察设计研究院 | Acidifying corrosion inhibitor for oil well and its preparation |
| CN1894389A (en) * | 2003-10-17 | 2007-01-10 | 弗劳尔科技公司 | Compositions, configurations, and methods of reducing naphthenic acid corrosivity |
| CN101875857A (en) * | 2009-04-30 | 2010-11-03 | 中国石油化工股份有限公司 | Method for reducing corrosivity of acidiferous distillate oil |
Non-Patent Citations (2)
| Title |
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| 环烷酸盐对环烷酸腐蚀性的影响及原因;王征 等;《石油学报》;20110625;第27卷(第3期);第461-464页 * |
| 环烷酸盐类的应用与生产;杨克训;《润滑油》;19941205(第6期);第43-46页 * |
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