CN101875857A - Method for reducing corrosivity of acidiferous distillate oil - Google Patents
Method for reducing corrosivity of acidiferous distillate oil Download PDFInfo
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- CN101875857A CN101875857A CN 200910135875 CN200910135875A CN101875857A CN 101875857 A CN101875857 A CN 101875857A CN 200910135875 CN200910135875 CN 200910135875 CN 200910135875 A CN200910135875 A CN 200910135875A CN 101875857 A CN101875857 A CN 101875857A
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Abstract
The invention provides a method for reducing corrosivity of acidiferous distillate oil. In the method, a corrosion inhibiting component is added into the acidiferous distillate oil, wherein the corrosion inhibiting component is crude oil or a crude oil distillate of which the total mass content of asphaltine and colloid is over 10 percent. The method adopts a component from the crude oil as a corrosion inhibitor, has the characteristics of convenient sources, high thermal stability and low price, can inhibit the corrosions, caused by acidiferous crude oil, to the parts such as a tower body of a vacuum tower, a filling material, a lateral line and the like, and can also inhibit the corrosion to metal equipment under other similar conditions.
Description
Technical field
The invention belongs to the crude oil manufacture field, particularly relate to the method that a kind of reduction contains the acid fraction oil corrosion.
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.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.
In the research aspect the application inhibiter inhibition naphthenic acid corrosion nearly 50 years history is arranged abroad, in early days mainly based on amine and acid amides, but therefore the decomposition easily at high temperature of this class inhibiter is replaced by other medicament gradually.According to the T-8 council of U.S. corrosion association investigation statistics, by the end of the year 1996, kind surplus the inhibiter patent relevant with naphthenic acid corrosion of having applied for reached 30, content relates to multiple organism such as N, P, S and composition thereof, in recent years along with the crude oil poor qualityization increases the weight of, the high-temperature naphthenic acid Research on Corrosion Inhibitor more and more receives publicity.
Petrolite company has applied for that in nineteen ninety phosphorous acid two (three) alkyl esters and thiazoline (2,2-pentylidene-4,5-tetramethylene-1,3-thiazoles quinoline) compound are used to suppress the patent (patent No. US4941994) of naphthenic acid high temperature corrosion.
Exxon company has applied for that in 1993 the organic polysulfide compound is used to suppress the patent (patent No. US5182013) of naphthenic acid high temperature corrosion.
The patent US5252254 of Nalco company has reported the restraining effect of sulfonated alkylphenol to the naphthenic acid high temperature corrosion.
The restraining effect of mercapto-triazine compound to the naphthenic acid high temperature corrosion reported at the patent US5464525 of nineteen ninety-five application in the Betz laboratory.
Luoyang Petrochemical engineering corporation of China Petrochemical Industry has reported that at the patent CN1035020 of application in 1997 alkyl phosphate and alkyl diazine ring system compounds compound copolymer suppress the effect of naphthenic acid corrosion.
Exxon-Mobil research and engineering corporation have reported the restraining effect of 4-sulfosalicylic phthalate to the naphthenic acid high temperature corrosion at the patent US6583091 of application in 2003, US6537950 has reported the restraining effect of triphenyl-stibine to the naphthenic acid high temperature corrosion, US6559104 has reported the restraining effect of three acidic functionality substituted benzenes to the naphthenic acid high temperature corrosion, compound has 5-hydroxyl-phthalic acid, 1,2,3-three phenylformic acid, 1,3,5-three phenylformic acid.The compound (alkyl phosphate, alkyl sulfuric ester, alkyl imidazoline) that the commercial N-5180 inhibiter of NALCO company is phosphoric acid ester-amine.
CN1894389A has described a kind of method that alleviates naphthenic acid corrosion, will contain the corrosion that weak erosive β acid fraction oil and severe corrosive a acid fraction oil mixed refining can alleviate naphthenic acid.
These high-temperature corrosion inhibitors are Chemicals or the composition that contains P, S, N, O element, have the high deficiency of use cost.
Summary of the invention
The invention provides the method that a kind of reduction contains the acid fraction oil corrosion, this method can suppress naphthenic acid corrosion to hardware under hot conditions.
A kind of reduction provided by the invention contains the method for acid fraction oil corrosion, comprising: the inhibition component is joined contain in the acid fraction oil, said inhibition component is bituminous matter and gelationus total mass content greater than 10% crude oil or crude oil fractions.
The said acid number (TAN) that contains acid fraction oil is at least 0.5mgKOH/g, even greater than 2.0mgKOH/g.The said acid fraction oil true boiling point that contains is smaller or equal to 530 ℃, and preferred 180 ℃～530 ℃, asphalt content is less than 0.1%.
Said bituminous matter is to be insoluble to small molecules normal paraffin (as pentane, heptane) in the oil and the material that is dissolved in benzene, is relative molecular mass maximum in the crude oil, non-hydrocarbon component that polarity is stronger.
Said colloid is firmly to be adsorbed in silica gel or aluminum oxide, non-hydrocarbon component that polarity is stronger in the crude oil except that bituminous matter, and true boiling point is greater than 530 ℃.
Said inhibition component is bituminous matter and gelationus total mass content greater than 10% crude oil or crude oil fractions.What specifically, said inhibition component can be bituminous matter and gelationus total mass content greater than in 10% crude oil, residual oil, solvent-deasphalted oils, de-oiled asphalt and bituminous matter of separating from crude oil and the colloid is at least a.Wherein, residual oil can obtain by distillation, reduced pressure distillation process process, and asphalt content is generally 0～40w%, and gum level is generally 10～50w%.Solvent-deasphalted oils is the derived product of vacuum residuum, can obtain by the solvent deasphalting technological process, and asphalt content is generally 0～2w%, and gum level is 10～40w%.De-oiled asphalt is the derived product of vacuum residuum, can obtain by the solvent deasphalting technological process, and asphalt content is generally 10～90w%, and gum level is generally 0～50w%.Isolating bitum method from crude oil can be with C
3～C
8Alkane (as pentane, heptane) is deviate from bituminous matter for solvent, and wherein the asphalt content maximum can reach 100w%.From crude oil, isolate the gelationus method and can obtain colloid by vacuum residuum and the alkane mixed solution of removing pitch prill matter carried out silica gel adsorption.
Said inhibition component can join contain acid fraction oil including but not limited in the appliance arrangements such as reactor, pipeline or storage tank, preferably the perishable position from appliance arrangement adds, it can be 100～600 ℃ that the inhibition component adds the fashionable temperature that contains acid fraction oil, preferred 180～350 ℃.
Said inhibition component is with respect to the quality that contains acid fraction oil, add-on is 5～20000mg/kg, preferably, the add-on of said inhibition component in containing acid fraction oil is that to make bituminous matter in the inhibition component and gelationus total content and the ratio of the quality that contains acid fraction oleic acid value be 0.002～2: 1, preferred 0.005～0.8: 1.
The inventor is unexpected in the naphthenic acid corrosion research process to find that bituminous matter in the crude oil and colloid have the good restraining effect to naphthenic acid corrosion.Adopt these components that come from the crude oil to have convenient sources, Heat stability is good, cheap characteristics as inhibiter.The inventive method can suppress the corrosion of acid-containing raw oil to positions such as ordinary decompression column tower body, filler and side lines, and the present invention is equally applicable to the protection against corrosion of the hardware of other conditions of similarities.
Embodiment
Corrosion test is carried out in the 500mL autoclave, with the weightless corrosion mitigating effect that characterizes of metal lacing film.
Test piece material: 20# carbon steel; Test temperature: 270～280 ℃; Test period: 2h
Following embodiment only is used to explain the present invention, and should not limit the scope of the invention.
Embodiment 1:
The acid-containing raw oil of corrosive medium: TAN=1.47mgOH/g is got 270～350 ℃ of cuts respectively and 350～530 ℃ of cuts carry out corrosion experiment.
The solvent-deasphalted oils that adopts vacuum residue fraction is as the inhibition component, and deasphalted oil character sees Table 1, and corrosion mitigating effect sees Table 2, and consumption ratio wherein is meant the ratio of bituminous matter in the inhibition component and gelationus total content and the quality that contains acid fraction oleic acid value, down with.
Table 1 deasphalted oil character
| Four components | ??w/％ |
| Saturated branch | ??23.2 |
| Fragrance divides | ??62.7 |
| Colloid | ??14.0 |
| Bituminous matter | ??＜0.1 |
Table 2 deasphalted oil corrosion mitigating effect
To 270～350 ℃ of distillates, when deasphalted oil adding concentration was 50mg/kg, erosion rate was reduced to 0.30mm/a from 0.75mm/a, and corrosion inhibition rate reaches 60.0%; 350～530 ℃ of distillates, when deasphalted oil adding concentration was 5000mg/kg, erosion rate was reduced to 0.35mm/a from 1.58mm/a, and corrosion inhibition rate reaches 77.8%.
Embodiment 2:
The high-acid crude oil of corrosive medium: TAN=6.24mgOH/g is got 270～350 ℃ of cuts respectively and 350～530 ℃ of cuts carry out corrosion experiment.
Adopt embodiment 1 deasphalted oil as the inhibition component, experimental result sees Table 3.To 270～350 ℃ of distillates, when deasphalted oil adding concentration was 200mg/kg, erosion rate was reduced to 0.45mm/a from 1.66mm/a, and corrosion inhibition rate reaches 72.9%; 350～530 ℃ of distillates, when deasphalted oil adding concentration was 10000mg/kg, erosion rate was reduced to 0.68mm/a from 3.47mm/a, and corrosion inhibition rate reaches 74.6%.
Table 6 deasphalted oil corrosion mitigating effect
Embodiment 3:
The acid-containing raw oil of corrosive medium: TAN=6.24mgOH/g is got 270～350 ℃ of cuts respectively and 350～530 ℃ of cuts carry out corrosion experiment.
Adopt de-oiled asphalt as the inhibition component, de-oiled asphalt character sees Table 4, and experimental result sees Table 5.To 270～350 ℃ of distillates, when de-oiled asphalt adding concentration was 20mg/kg, erosion rate was reduced to 0.75mm/a from 1.66mm/a, and corrosion inhibition rate reaches 54.8%; 350～530 ℃ of distillates, when de-oiled asphalt adding concentration was 2000mg/kg, erosion rate was reduced to 0.68mm/a from 3.47mm/a, and corrosion inhibition rate reaches 80.4%.
Table 4 de-oiled asphalt character
| Four components | ??w/％ |
| Saturated branch+fragrance divides | ??16.2 |
| Colloid | ??14.0 |
| Bituminous matter | ??69.8 |
Table 5 de-oiled asphalt corrosion mitigating effect
Embodiment 4:
Corrosive medium: get 270～350 ℃ of distillates and carry out corrosion experiment, TAN=4.27mgOH/g, employing from vacuum residuum isolated colloid as the inhibition component, corrosion mitigating effect sees Table 6, when colloid adding concentration is 50mg/kg, the erosion rate of distillate is reduced to 1.41mm/a from 3.95mm/a, and corrosion inhibition rate reaches 64.3%; When colloid adding concentration was 2000mg/kg, erosion rate was reduced to 0.99mm/a, and corrosion inhibition rate reaches 74.9%.The gelationus separation method is: in the vacuum residuum of removing pitch prill matter and Skellysolve A mixed solution, add grain through being 60-100 purpose tlc silica gel, the silica gel consumption is a 1g residual oil: 5g silica gel.The mixture of stirred liq and silica gel, vacuum filtration, the silica gel of adsorption gel washes about 10 times repeatedly with the mixed solution flushing of 7% methyl alcohol and methylene dichloride,, near colourless washing fluid is placed on the rotatory evaporator up to washing fluid, steams solvent, obtains colloid.
Table 6 colloid corrosion mitigating effect
Embodiment 5:
The high-acid crude oil of corrosive medium: TAN=10.53mgOH/g is got 220～270 ℃ of cuts, 270～350 ℃ of cuts and 350～530 ℃ of cuts respectively and is carried out corrosion experiment.
Adopt vacuum residuum as the inhibition component, vacuum residuum character sees Table 7, and experimental result sees Table 8.To 220～270 ℃ of distillates, when vacuum residuum adding concentration was 30mg/kg, erosion rate was reduced to 0.44mm/a from 1.27mm/a, and corrosion inhibition rate reaches 65.4%; To 270～350 ℃ of distillates, when vacuum residuum adding concentration was 100mg/kg, erosion rate was reduced to 0.52mm/a from 2.13mm/a, and corrosion inhibition rate reaches 75.6%; 350～530 ℃ of distillates, when vacuum residuum adding concentration was 2000mg/kg, erosion rate was reduced to 0.88mm/a from 3.48mm/a, and corrosion inhibition rate reaches 74.7%.
Table 7 vacuum residuum character
| Four components | ??w/％ |
| Saturated branch | ??23.4 |
| Fragrance divides | ??32.1 |
| Colloid | ??44.5 |
| Bituminous matter | ??＜0.1 |
Table 8 vacuum residuum corrosion mitigating effect
Embodiment 6:
The high-acid crude oil of corrosive medium: TAN=10.53mgOH/g is got 270～350 ℃ of cuts respectively and 350～530 ℃ of cuts carry out corrosion experiment.
Adopt the heptane bituminous matter as the inhibition component, experimental result sees Table 9.To 270～350 ℃ of distillates, when heptane bituminous matter adding concentration was 50mg/kg, erosion rate was reduced to 0.49mm/a from 2.13mm/a, and corrosion inhibition rate reaches 77.0%; 350～530 ℃ of distillates, when heptane bituminous matter adding concentration was 500mg/kg, erosion rate was reduced to 0.82mm/a from 3.48mm/a, and corrosion inhibition rate reaches 76.4%.
Table 9 heptane bituminous matter corrosion mitigating effect
Embodiment 7:
The high-acid crude oil of corrosive medium: TAN=10.53mgOH/g is got 270～350 ℃ of cuts respectively and 350～530 ℃ of cuts carry out corrosion experiment.
Adopt crude oil as the inhibition component, the crude oil oil nature sees Table 10, and experimental result sees Table 11.To 270～350 ℃ of distillates, when crude oil adding concentration was 100mg/kg, erosion rate was reduced to 0.74mm/a from 2.13mm/a, and corrosion inhibition rate reaches 65.2%; 350～530 ℃ of distillates, when crude oil adding concentration was 2000mg/kg, erosion rate was reduced to 1.68mm/a from 3.48mm/a, and corrosion inhibition rate reaches 51.7%.
Table 10 oil property
| Four components | ??w/％ |
| Saturated branch | ??25.6 |
| Fragrance divides | ??38.7 |
| Colloid | ??24.5 |
| Bituminous matter | ??11.2 |
Table 11 crude oil corrosion mitigating effect
Claims (12)
1. a reduction contains the method for acid fraction oil corrosion, comprising: the inhibition component is added the people to containing in the acid fraction oil, and said inhibition component is bituminous matter and gelationus total mass content greater than 10% crude oil or crude oil fractions.
2. in accordance with the method for claim 1, it is characterized in that the said acid number that contains acid fraction oil is at least 0.5mgKOH/g.
3. in accordance with the method for claim 1, it is characterized in that the said acid fraction oil true boiling point that contains is smaller or equal to 530 ℃, asphalt content is less than 0.1%.
4. in accordance with the method for claim 1, it is characterized in that said colloid true boiling point is greater than 530 ℃.
5. in accordance with the method for claim 1, it is characterized in that what said inhibition component was bituminous matter and gelationus total mass content greater than in 10% crude oil, residual oil, solvent-deasphalted oils, de-oiled asphalt and bituminous matter of separating and the colloid is at least a from crude oil.
6. in accordance with the method for claim 1, it is characterized in that said inhibition component joins in the appliance arrangement including but not limited to reactor, pipeline or storage tank that contains acid fraction oil.
7. in accordance with the method for claim 6, it is characterized in that said inhibition component adds from the perishable position of appliance arrangement.
8. according to claim 1 or 7 described methods, it is characterized in that it is 100～600 ℃ that the inhibition component adds the fashionable temperature that contains acid fraction oil
9. in accordance with the method for claim 1, it is characterized in that it is 180～350 ℃ that the inhibition component adds the fashionable temperature that contains acid fraction oil.
10. in accordance with the method for claim 1, it is characterized in that said inhibition component is with respect to the quality that contains acid fraction oil, add-on is 5～20000mg/kg.
11. in accordance with the method for claim 1, it is characterized in that the add-on of said inhibition component in containing acid fraction oil is that to make bituminous matter in the inhibition component and gelationus total content and the ratio of the quality that contains acid fraction oleic acid value be 0.002～2: 1.
12. in accordance with the method for claim 1, it is characterized in that the add-on of said inhibition component in containing acid fraction oil is that to make bituminous matter in the inhibition component and gelationus total content and the ratio of the quality that contains acid fraction oleic acid value be 0.005～0.8: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994149A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Corrosion-retarding agent and preparation method thereof, and method for reducing acid-containing hydrocarbon oil corrosivity |
| CN104560199A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Corrosion inhibitor composition and method inhibiting naphthenic acid corrosion of oil refining device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5630964A (en) * | 1995-05-10 | 1997-05-20 | Nalco/Exxon Energy Chemicals, L.P. | Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack |
| FR2857372B1 (en) * | 2003-07-07 | 2005-08-26 | Atofina | METHOD FOR CONTROLLING CORROSION BY NAPHTHENIC ACIDS IN REFINERIES |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994149A (en) * | 2011-09-08 | 2013-03-27 | 中国石油化工股份有限公司 | Corrosion-retarding agent and preparation method thereof, and method for reducing acid-containing hydrocarbon oil corrosivity |
| CN102994149B (en) * | 2011-09-08 | 2015-03-18 | 中国石油化工股份有限公司 | Corrosion-retarding agent and preparation method thereof, and method for reducing acid-containing hydrocarbon oil corrosivity |
| CN104560199A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Corrosion inhibitor composition and method inhibiting naphthenic acid corrosion of oil refining device |
| CN104560199B (en) * | 2013-10-12 | 2016-01-13 | 中国石油化工股份有限公司 | The method of composite corrosion inhibitor and suppression oil refining apparatus naphthenic acid corrosion |
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