CN102220162A - Method for reducing corrosivity of crude oil - Google Patents
Method for reducing corrosivity of crude oil Download PDFInfo
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- CN102220162A CN102220162A CN2010101470824A CN201010147082A CN102220162A CN 102220162 A CN102220162 A CN 102220162A CN 2010101470824 A CN2010101470824 A CN 2010101470824A CN 201010147082 A CN201010147082 A CN 201010147082A CN 102220162 A CN102220162 A CN 102220162A
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Abstract
The invention relates to a method for reducing the corrosivity of crude oil, which comprises the following steps of: heating the crude oil with the organochlorine content larger than or equal to 5mg/kg to 60-200 DEG C, reacting for 0.5-24 hours, then mixing with an emulsion breaker and water, and finally separating out an oil phase after demulsification and dehydration under the action of an electric field. By adopting the method, the naphthenic acid corrosion of the crude oil can be reduced.
Description
Technical field
The present invention relates to the corrosive method of a kind of reduction crude oil.
Background technology
Contain organic acid in the crude oil, in Crude Oil Processing, can cause the corrosion of equipment.Usually naphthenic acid accounts for more than 85% of organic acid total amount in the crude oil, is to cause refining equipment corrosive principal element.The naphthenic acid corrosion characteristic is different with sulfur corrosion, and the naphthenic acid corrosion form is spot corrosion, pitting corrosion and grooving corrosion, very easily causes equipment perforation or breaks, and causes material to reveal major accidents such as initiation fire.Though the naphthenic acid corrosion problem found for eight more than ten years, because naphthenic acid is comparatively complicated to the mechanism of corrosion of equipment, people also lack deep understanding and understanding to this, make naphthenic acid corrosion become and are difficult to prediction and control.
At present, adopt following several method reply naphthenic acid corrosion: the upgrading of (1) equipment and materials; (2) crude oil mixing is to reduce the total acid value of crude oil; (3) annotate inhibiter.Wherein crude oil mixing is the most a kind of method of extensive employing, be about to contain acid or high-acid crude oil and low sour crude oil mixing, the commingled crude acid number is lower than below the threshold value 0.5mgKOH/g of naphthenic acid corrosion generation, but threshold value only is an empirical value in processing acid-containing raw oil process.Because also not deep to the mechanism of corrosion of naphthenic acid understanding, when oil property changes, even total acid value less than 0.5mgKOH/g, heavy corrosion also takes place in some positions of processing unit (plant), this also is a problem that always perplexs oil refining enterprise.
Summary of the invention
The invention provides the corrosive method of a kind of reduction crude oil, comprising: the acid-containing raw oil of content of organic chloride 〉=5mg/kg is heated to 60～200 ℃, behind reaction 0.5～24h, mixes, under electric field action, behind the breaking emulsion and dewatering, isolate oil phase with emulsion splitter and water.
Described content of organic chloride is meant in the crude oil, the content of the chlorine that exists with the organic compound form.
The content of organic chloride of described crude oil is preferred 〉=10mg/kg, more preferably 〉=20mg/kg, most preferably 〉=30mg/kg.
Preferably under the situation, with heating crude oil to 100～200 ℃.
Preferably under the situation, with heating crude oil reaction 0.5～10h.
Described crude oil comprises the low sour crude oil of acid number (TAN)＜0.5mgKOH/g, the acid-containing raw oil of acid number 0.5～2.0mgKOH/g, and the high-acid crude oil of acid number 〉=2.0mgKOH/g.The acid number of described crude oil is preferred 〉=0.5mgKOH/g, more preferably 〉=acid number 1mgKOH/g, most preferably 〉=2.0mgKOH/g.
The present invention has no particular limits emulsion splitter, can adopt the emulsion splitter of this area routine.
Those skilled in the art know how to carry out breaking emulsion and dewatering under electric field action.Generally speaking, be benchmark with the quality of crude oil, the consumption of emulsion splitter is 10～200 μ g/g, preferred 30～100 μ g/g; Quality with crude oil is a benchmark, and the consumption of water is 3%～20%, preferred 5%～10%; The temperature range of breaking emulsion and dewatering is 90～145 ℃, preferred 110～140 ℃; Electric-force gradient is 200～800V/cm.
Under the preferred situation, the present invention utilizes the electric desalting process of refinery to carry out breaking emulsion and dewatering after described heating crude oil is handled, and promptly utilizes the electric desalting apparatus of refinery and technology of electric de-salting to come breaking emulsion and dewatering, separately procuring equipment or device for modifying.
In the naphthenic acid corrosion research process, the inventor finds, organic compound chloride in the crude oil can generate quaternary ammonium compound with the nitrogenous compound reaction in the crude oil, this quaternary ammonium compound has tangible strengthening effect to the corrosion of naphthenic acid, naphthenic acid corrosion occurs in more than 200 ℃, this quaterisation temperature is then lower, be easy to carry out under heating condition, and therefore chloride organic compound has bigger hazardness to Crude Oil Processing.The present invention is based on the new knowledge of organochlorine promotion naphthenic acid corrosion, employing will contain the crude oil elder generation heat pre-treatment of organochlorine, chloride organic compound and the nitrogenous compound in the crude oil are fully reacted generate water-soluble quaternary ammonium salt, and by the content of organic chloride in the method reduction crude oil of electric desalting, thereby reduce Crude Oil Corrosivity.
Embodiment
Further specify the present invention by the following examples.
Embodiment one
Used total acid mumber of crude oil TAN=1.75, total nitrogen content 0.25%, density 0.9331g/cm
3, chloride content 45mg/Kg.
With heating crude oil to 120 ℃, insulation 4h carries out quaterisation, carries out desalting treatment then, and the desalination condition is: injection rate 10%, emulsion splitter dosage 50ppm.The emulsion splitter aqueous solution for preparing was in advance mixed on commercially available juice extractor 20 seconds with crude oil, adopt DP-2C emulsion splitter competition instrument to carry out oily water separation, strength of electric field 300V/cm, 95 ℃ of temperature, after the oily water separation, draw oil sample by add emulsion splitter and water filling washing twice with quadrat method, get upper strata oil and survey chloride content.The contrast experiment be heating crude oil to 90 ℃ immediately with the emulsion splitter aqueous solution, handle by same desalination condition.Experimental result sees Table 1, and as can be seen, the contrast experiment takes off the total chlorine in back and still has 16mg/Kg (content of organic chloride), and erosion rate is 0.68mm/a, and crude oil total chlorine after preheating treatment process is reduced to 6.6mg/Kg, and erosion rate is reduced to 0.29mm/a.
Table 1
Embodiment two
Used total acid mumber of crude oil TAN=3.47, total nitrogen content 0.37%, chloride content 95mg/Kg.
With heating crude oil to 180 ℃, insulation 1h carries out quaterisation, carries out desalting treatment then, and the desalination condition is: injection rate 10%, emulsion splitter dosage 50ppm.The emulsion splitter aqueous solution for preparing was in advance mixed on commercially available juice extractor 20 seconds with crude oil, adopt DP-2C emulsion splitter competition instrument to carry out oily water separation, strength of electric field 300V/cm, 95 ℃ of temperature, after the oily water separation, draw oil sample by add emulsion splitter and water filling washing twice with quadrat method, get upper strata oil and survey chloride content.The contrast experiment be heating crude oil to 90 ℃ immediately with the emulsion splitter aqueous solution, handle by same desalination condition.Experimental result sees Table 2, and as can be seen, the contrast experiment takes off the total chlorine in back and still has 38mg/Kg (content of organic chloride), and erosion rate is 0.68mm/a, and crude oil total chlorine after preheating treatment process is reduced to 8.8mg/Kg, and erosion rate is reduced to 0.29mm/a.
Table 2
Claims (11)
1. one kind is reduced the corrosive method of crude oil, comprising: with heating crude oil to 60～200 of content of organic chloride 〉=5mg/kg ℃, behind reaction 0.5～24h, mix with emulsion splitter and water, behind the breaking emulsion and dewatering, isolate oil phase under electric field action.
2. in accordance with the method for claim 1, it is characterized in that the content of organic chloride 〉=10mg/kg of described crude oil.
3. in accordance with the method for claim 2, it is characterized in that the content of organic chloride 〉=20mg/kg of described crude oil.
4. in accordance with the method for claim 3, it is characterized in that the content of organic chloride 〉=30mg/kg of described crude oil.
5. in accordance with the method for claim 1, it is characterized in that, heating crude oil to 100～200 ℃.
6. in accordance with the method for claim 5, it is characterized in that, heating crude oil reaction 0.5～10h.
7. in accordance with the method for claim 1, it is characterized in that the acid number 〉=0.5mgKOH/g of described crude oil.
8. in accordance with the method for claim 7, it is characterized in that the acid number 〉=1mgKOH/g of described crude oil.
9. in accordance with the method for claim 8, it is characterized in that the acid number 〉=2.0mgKOH/g of described crude oil.
10. in accordance with the method for claim 1, it is characterized in that, is benchmark with the quality of crude oil, and the consumption of emulsion splitter is 10～200 μ g/g; Quality with crude oil is a benchmark, and the consumption of water is 3%～20%; The temperature range of breaking emulsion and dewatering is 90～145 ℃; Electric-force gradient is 200～800V/cm.
11. in accordance with the method for claim 1, it is characterized in that, utilize the electric desalting process of refinery to carry out breaking emulsion and dewatering.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010147082.4A CN102220162B (en) | 2010-04-15 | 2010-04-15 | Method for reducing corrosivity of crude oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937532A (en) * | 2014-05-05 | 2014-07-23 | 碧海舟（北京）石油化工设备有限公司 | Device and method for heated dehydration of crude oil |
| CN105480607A (en) * | 2016-01-06 | 2016-04-13 | 山东普利龙压力容器有限公司 | Internal oil tank heating oil product quality control system and quality control method |
| CN106675619A (en) * | 2016-07-19 | 2017-05-17 | 辽宁石油化工大学 | Method for removing nitride in diesel fraction of shale oil by quaterisation reaction |
| CN108611112A (en) * | 2018-06-05 | 2018-10-02 | 陕西煤业化工集团神木天元化工有限公司 | The method and system of coal tar dehydration |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418934A (en) * | 2001-11-14 | 2003-05-21 | 中国石化集团洛阳石油化工工程公司设备研究所 | Techonlogical method for removing naphthenic acid from crude oil and distillated oil |
| FR2883571A1 (en) * | 2005-03-23 | 2006-09-29 | Petroleo Brasileiro Sa | Reducing naphthenic acidity in petroleum oil comprises providing oil, supplying oil with water towards radiation emitter, decomposing carboxylic acids to liberate carbon dioxide, separating gas, water and oil phases, and recovering oil |
| CN101037612A (en) * | 2007-04-29 | 2007-09-19 | 中国石油化工股份有限公司 | Crude oil pulsing electrical desalting technique |
-
2010
- 2010-04-15 CN CN201010147082.4A patent/CN102220162B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418934A (en) * | 2001-11-14 | 2003-05-21 | 中国石化集团洛阳石油化工工程公司设备研究所 | Techonlogical method for removing naphthenic acid from crude oil and distillated oil |
| FR2883571A1 (en) * | 2005-03-23 | 2006-09-29 | Petroleo Brasileiro Sa | Reducing naphthenic acidity in petroleum oil comprises providing oil, supplying oil with water towards radiation emitter, decomposing carboxylic acids to liberate carbon dioxide, separating gas, water and oil phases, and recovering oil |
| CN101037612A (en) * | 2007-04-29 | 2007-09-19 | 中国石油化工股份有限公司 | Crude oil pulsing electrical desalting technique |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937532A (en) * | 2014-05-05 | 2014-07-23 | 碧海舟（北京）石油化工设备有限公司 | Device and method for heated dehydration of crude oil |
| CN103937532B (en) * | 2014-05-05 | 2016-05-11 | 碧海舟（北京）石油化工设备有限公司 | Heating crude oil dewater unit and method |
| CN105480607A (en) * | 2016-01-06 | 2016-04-13 | 山东普利龙压力容器有限公司 | Internal oil tank heating oil product quality control system and quality control method |
| CN105480607B (en) * | 2016-01-06 | 2018-02-13 | 山东普利龙压力容器有限公司 | Built-in oil tank heating oil quality control system and method for quality control |
| CN106675619A (en) * | 2016-07-19 | 2017-05-17 | 辽宁石油化工大学 | Method for removing nitride in diesel fraction of shale oil by quaterisation reaction |
| CN106675619B (en) * | 2016-07-19 | 2018-12-07 | 辽宁石油化工大学 | The method that quaternization reaction removes nitride in shale oil diesel oil distillate |
| CN108611112A (en) * | 2018-06-05 | 2018-10-02 | 陕西煤业化工集团神木天元化工有限公司 | The method and system of coal tar dehydration |
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| CN102220162B (en) | 2014-03-12 |
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