CN101987973B - Method for reducing corrosivity of acid-contained hydrocarbon oil - Google Patents
Method for reducing corrosivity of acid-contained hydrocarbon oil Download PDFInfo
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- CN101987973B CN101987973B CN200910157463.8A CN200910157463A CN101987973B CN 101987973 B CN101987973 B CN 101987973B CN 200910157463 A CN200910157463 A CN 200910157463A CN 101987973 B CN101987973 B CN 101987973B
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Abstract
The invention relates to a method for reducing the corrosivity of acid-contained hydrocarbon oil, comprising the following steps of: adding corrosion inhibition components to the acid-contained hydrocarbon oil, and the corrosion inhibition components are crude oil and distillate oil, the asphaltene content of which is greater than the acid-contained hydrocarbon oil. Naphthenic acid can be effectively inhibited from corroding metal equipment by adopting the method.
Description
Technical field
The present invention relates to a kind of corrosive method of reduction acid-containing hydrocarbon oil.
Background technology
In recent years, global heavy, crude oil with poor quality output increased sharply, and accounted for global crude oil ratio and rose year by year, but were subject to the restriction of oil refining apparatus process conditions, and demand growth is slow, and therefore price poor quality widens gradually.At Processing HA Oil under High Oil Price, there is certain cost advantage, but when processing contains acid or high-acid crude oil, one of the most scabrous problem is the corrosion of aphthenic acids 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 regime, is optimized design to refining equipment structure; (3) improve refining process process, as crude oil mixing, crude oil deacidification, to perishable position filling corrosion inhibiter etc.At present, crude oil mixing is a kind of method that domestic refining high-acid crude oil the most extensively adopts, be about to contain acid or high-acid crude oil and low sour crude oil mix, make below the critical value 0.5mgKOH/g that mixed crude acid number occurs lower than naphthenic acid corrosion, but critical value is only empirical value in processing acid-containing raw oil process.Due to also not deep to the corrosion mechanism understanding of aphthenic acids, when oil property changes, even if total acid number is less than 0.5mgK0H/g, also there is heavy corrosion in some positions of processing unit (plant).In high-acid crude oil refining process, also find that the corrosivity of crude oil to processing unit (plant) that total acid number is identical also differs widely, be the aphthenic acids composition difference of different crude oils to the understanding that this phenomenon is more general, aphthenic acids architectural difference is the main cause causing crude oil corrosivity different; But aphthenic acids composition is complicated, accurately determines that aphthenic acids forms and the corrosivity relation set up correspondingly is very difficult, therefore current total acid number remains and judges the corrosive unique foundation of crude oil, is also unique guide parameters of crude oil mixing.
Summary of the invention
The invention provides a kind of corrosive method of reduction acid-containing hydrocarbon oil, the method can suppress aphthenic acids to the corrosion of hardware.
Method of the present invention comprises: join in acid-containing hydrocarbon oil by inhibition component, and inhibition component is crude oil and the distillate that asphalt content is greater than acid-containing hydrocarbon oil.
Described acid-containing hydrocarbon oil is topped crude or reduced crude at the bottom of crude oil, primary distillation tower.Topped crude at the bottom of primary distillation tower refers to before crude oil atmospheric distillation, the product obtained after the carburet hydrogen in crude oil, part light component and a small amount of moisture being steamed.
The acid number (TAN) of described acid-containing hydrocarbon oil preferably >=0.5mgKOH/g, more preferably >=1.0mgKOH/g.
Described inhibition component is preferably one or more in crude oil, residual oil and solvent deoiling pitch.Wherein, residual oil can be obtained by air-distillation, reduced pressure distillation process process, and asphalt content is generally 0 ~ 40%; Solvent deoiling pitch can be obtained by solvent de-asphalting process process, and deasphalting solvent can be propane, butane, pentane, heptane, and asphalt content is generally 10 ~ 100%.
Preferably, in mass percentage, the asphalt content of inhibition component is at least higher by 10% than the asphalt content of acid-containing raw oil; More preferably, the asphalt content of inhibition component is at least higher by 20% than the asphalt content of acid-containing raw oil.
Temperature range of the present invention is preferably 100 ~ 600 DEG C, is more preferably 180 ~ 350 DEG C.
With the quality of acid-containing raw oil for benchmark, inhibition component addition is preferably 0.5 ~ 10%.
The asphalt content of inhibition component and acid-containing hydrocarbon oil mixture and the ratio of acid-containing hydrocarbon oil acid number are preferably 1 ~ 20, and be more preferably 2 ~ 10, wherein the unit of acid number is mgKOH/g, and the unit of asphalt content is mg/g.
The present invention adopts asphalt content to be greater than the crude oil of acid-containing hydrocarbon oil and distillate as corrosion inhibiter, aphthenic acids not only effectively can be suppressed the corrosion of hardware, and have convenient sources, cheap advantage.
Detailed description of the invention
Corrosion test is carried out in 500mL autoclave, characterizes corrosion mitigating effect with metal weight loss.
Test piece material: 20# carbon steel
Test temperature: 270 ~ 280 DEG C
Test period: 2h
In embodiment, asphalt content all adopts the method for RIPP 10-90 to measure.
Embodiment 1
Acid-containing raw oil total acid number TAN=3.56, asphalt content < 0.1%, the crude oil being 18.5% with asphalt content mixes, mixed proportion is weight ratio 9: 1, make acid-containing raw oil studies on asphaltene content reach 1.85%, the asphalt content of inhibition component and acid-containing raw oil mixture and the ratio of acid-containing raw oil acid number are 5.2: 1.
After mixing, the corrosion rate of acid-containing raw oil is reduced to 0.47mm/a from the 0.92mm/a of former acid-containing raw oil.
Embodiment 2
Acid-containing raw oil total acid number TAN=1.75, asphalt content 0.28%, the decompression residuum being 36.7% with asphalt content mixes, mixed proportion is weight ratio 30: 1, make acid-containing raw oil studies on asphaltene content reach 1.45%, the asphalt content of inhibition component and acid-containing raw oil mixture and the ratio of acid-containing raw oil acid number are 8.3: 1.
After mixing, the corrosion rate of acid-containing raw oil is reduced to 0.37mm/a from the 0.68mm/a of former acid-containing raw oil.
Embodiment 3
Acid-containing raw oil total acid number TAN=4.56, asphalt content 0.9%, the butane de-oiled asphalt being 68.7% with asphalt content mixes, mixed proportion is weight ratio 60: 1, make acid-containing raw oil studies on asphaltene content reach 2.01%, the asphalt content of inhibition component and acid-containing raw oil mixture and the ratio of acid-containing raw oil acid number are 4.4: 1.
After mixing, the corrosion rate of acid-containing raw oil is reduced to 0.45mm/a from the 0.88mm/a of former acid-containing raw oil.
Embodiment 4
Acid-containing raw oil total acid number TAN=3.56, asphalt content < 0.1%, mix with heptane pitch, mixed proportion is weight ratio 99: 1, make acid-containing raw oil studies on asphaltene content reach 1.00%, the asphalt content of inhibition component and acid-containing raw oil mixture and the ratio of acid-containing raw oil acid number are 2.8: 1.
After mixing, the corrosion rate of acid-containing raw oil is reduced to 0.52mm/a from the 0.92mm/a of former acid-containing raw oil.
Claims (7)
1. one kind is reduced the corrosive method of acid-containing hydrocarbon oil, comprise: inhibition component is joined in acid-containing hydrocarbon oil, described inhibition component is one or more in crude oil, residual oil and solvent deoiling pitch, in mass percentage, the asphalt content of inhibition component is at least higher by 10% than the asphalt content of acid-containing raw oil; Acid number >=the 0.5mgKOH/g of described acid-containing hydrocarbon oil; With the quality of acid-containing raw oil for benchmark, inhibition component addition is 0.5 ~ 10%; The asphalt content of inhibition component and acid-containing hydrocarbon oil mixture and the ratio of acid-containing hydrocarbon oil acid number are 1 ~ 20.
2. in accordance with the method for claim 1, it is characterized in that, described acid-containing hydrocarbon oil is topped crude or reduced crude at the bottom of crude oil, primary distillation tower.
3. in accordance with the method for claim 1, it is characterized in that, the acid number >=1.0mgKOH/g of described acid-containing hydrocarbon oil.
4. in accordance with the method for claim 1, it is characterized in that, the asphalt content of inhibition component is at least higher by 20% than the asphalt content of acid-containing raw oil.
5. in accordance with the method for claim 1, it is characterized in that, adding temperature is 100 ~ 600 DEG C.
6. in accordance with the method for claim 5, it is characterized in that, adding temperature is 180 ~ 350 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, the asphalt content of inhibition component and acid-containing hydrocarbon oil mixture and the ratio of acid-containing hydrocarbon oil acid number are 2 ~ 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910157463.8A CN101987973B (en) | 2009-07-30 | 2009-07-30 | Method for reducing corrosivity of acid-contained hydrocarbon oil |
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| CN200910157463.8A CN101987973B (en) | 2009-07-30 | 2009-07-30 | Method for reducing corrosivity of acid-contained hydrocarbon oil |
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| CN101987973A CN101987973A (en) | 2011-03-23 |
| CN101987973B true CN101987973B (en) | 2015-04-29 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101316915A (en) * | 2005-11-30 | 2008-12-03 | 贝克休斯公司 | Corrosion inhibitor |
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| US20060091044A1 (en) * | 2004-11-02 | 2006-05-04 | General Electric Company | High temperature corrosion inhibitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101316915A (en) * | 2005-11-30 | 2008-12-03 | 贝克休斯公司 | Corrosion inhibitor |
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| Title |
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| 提高油田集输管线石油沥青防腐质量;郑大铳 等;《内蒙古石油化工》;20051231(第8期);145 * |
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