CN103450925A - Crude oil complexing decalcification method - Google Patents
Crude oil complexing decalcification method Download PDFInfo
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- CN103450925A CN103450925A CN2012101684184A CN201210168418A CN103450925A CN 103450925 A CN103450925 A CN 103450925A CN 2012101684184 A CN2012101684184 A CN 2012101684184A CN 201210168418 A CN201210168418 A CN 201210168418A CN 103450925 A CN103450925 A CN 103450925A
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- nitrilotriacetic acid
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Abstract
The invention relates to a crude oil complexing decalcification method, which comprises: firstly placing nitrilotriacetic acid in water and conducting stirring constantly, adding an ammonia solution into the water in a dropwise manner gradually or by fed batch till the nitrilotriacetic acid is dissolved completely so as to obtain a decalcifying agent solution, mixing the solution, crude oil and a demulsifier fully and performing emulsification, carrying out oil-water separation after demulsification. The dosage of the nitrilotriacetic acid is 0.9-5.0 times of the mole number of metal calcium in the crude oil. The crude oil and the decalcifying agent are in a mass action ratio of 0.03-0.15. The adding amount of the demulsifier accounts for 20-50ppm of the quality of the crude oil. The method can remove more than 90% of calcium in the crude oil, has no secondary metal pollution to decalcified crude oil, has no corrosion to equipment, and generates no calcium sediment unfavorable to the process.
Description
Technical field
The present invention relates to a kind of crude oil complexing decalcification method, more particularly, is to utilize a kind of chemical agent to carry out the method for crude oil decalcifying.
Background technology
Calcium metal in crude oil is processed with considerable influence to crude oil, and in petrochemical industry, it is representative in the demetalization technology that it removes technology.Known chemical method crude oil decalcifying technology roughly can be summed up as chemical acid treatment decalcification method and chemical precipitation decalcification method, chelating decalcification method.The disclosed crude oil decalcifying technology such as CN1112424C, CN1454967A belongs to chemical acidic treatment, this class technology is to utilize the petroleum acid calcium principle in strong acid displacement crude oil in organic or inorganic to remove the calcium in crude oil, although disposable crude oil decalcifying rate is up to more than 90%, but shortcoming is that the industrial acids adopted is unfriendly to environment, industrial equipments is had to corrosive nature, need to select corrosion resistant apparatus, CN1055552A, CN1054261A, CN1078234C, the disclosed crude oil decalcifying technology such as ZL2005100707973 belongs to chemical precipitation method, these class methods adopt water soluble sulfate, phosphoric acid salt, petroleum acid calcium effect in phosphoric acid hydrogen disalt and crude oil generates slightly soluble or water-fast calcium sulfate, calcium phosphate, secondary calcium phosphate, under the effect of solid wetting agent, be deposited on water and reach the decalcification purpose, this method is comparatively friendly to environment and equipment, weak point is that consumption of chemical agent is large, the throw out produced for the decalcification reaction need to be processed with special separating device.
Crude oil chelating decalcification method also claims the complexing decalcification method, as disclosed crude oil decalcifying technology such as CN8610728A, CN1036981A, CN87105863, its adopt can with crude oil in the Ca aminocarboxylic acid, di-carboxylic acid, hydroxycarboxylic acid etc. that generate water soluble complex carry out crude oil decalcifying.Existing complexing decalcifying agent is generally containing carboxyl, hydroxyl, and the organic acid of the functional groups such as amino, it in use still has certain corrosion to hardware, therefore, is necessary that exploitation is to the free from corrosion complexing decalcification method of hardware.
Summary of the invention
The purpose of this invention is to provide a kind of crude oil complexing decalcification method, the method adopts carries out crude oil complexing decalcification to the free from corrosion chemical agent of equipment.
A kind of crude oil complexing decalcification method provided by the invention comprises: at first nitrilotriacetic acid(NTA) is placed in to water and constantly stirs, Xiang Shuizhong drips gradually or stream adds ammonia solution, all dissolve to nitrilotriacetic acid(NTA), obtain decalcifying agent solution, by this liquid with crude oil and emulsion splitter, fully mix, emulsification, oily water separation after breakdown of emulsion.
In the present invention, nitrilotriacetic acid(NTA) and ammonia effect generate the nitrilotriacetic acid(NTA) ammonium salt, and the pH value of its solution, between 9.0～10.0, is a kind of good calcium ion complexing agent, and simultaneously, this solution is corrosion-free to hardware, and the decalcification process does not produce throw out.
The consumption of nitrilotriacetic acid(NTA) is 0.9～5.0 times of calcium metal mole number in crude oil, is preferably 1.0～2.0 times.Ammoniacal liquor is the commodity ammonia solution, and its concentration is not particularly limited, generally 10～40%.Agent oil quality effect ratio is 0.03～0.15.
The operative temperature of crude oil and decalcifying agent, based on crude viscosity and determining, be greater than 40mm for 100 ℃ of kinematic viscosity
2the crude oil of/s, operative temperature is generally at 100 ℃～160 ℃; Be less than 40mm for 100 ℃ of kinematic viscosity
2the crude oil of/s, operative temperature is generally in normal temperature～100 ℃.
Emulsion splitter is that this area is general, the screening of based on crude kind, and effect is to promote oily water separation, its add-on generally accounts for 20～50ppm of crude quality.Emulsion splitter joins in decalcifying agent solution in advance, by decalcifying agent solution, enters crude oil.
The method of the invention can remove the calcium more than 90% in crude oil, crude oil after de-is not produced to secondary metals and pollute, corrosion-free to equipment, does not produce the disadvantageous calcium sediment of technique.
The method of the invention can be combined with refinery's technology of electric de-salting, and the decalcification rate is high.
Embodiment
Below with embodiment, the present invention is further described.
Embodiment 1:
Experiment is Kelamayi Jiu Qu crude oil with oil, and calcium contents is 220ppm, and its 100 ℃ of kinematic viscosity are 54mm
2/ s, nitrilotriacetic acid(NTA) is industrial goods, ammonia concn 25%.
By the agent oil quality, than 0.05, the nitrilotriacetic acid(NTA) amount is 1.8 times of preparation decalcifying agents of calcium metal mole number in crude oil, and emulsion splitter FC-9301 adds wherein, concentration 0.1%.Under constantly stirring, adjust decalcifying agent pH to 9.5 with ammoniacal liquor, nitrilotriacetic acid(NTA) all dissolves, and obtains decalcifying agent solution.Agent oil is mixed into electrodesalting and electrodehydrating instrument effect 30 minutes at 120 ℃, is purified oil, and by analysis, its calcium contents is 12.5ppm, decalcification rate 94.3%.
Embodiment 2:
Experiment is Kelamayi Jiu Qu and the western commingled crude of stone with oil, and calcium contents is that its 100 ℃ of kinematic viscosity of 102ppm are 12mm
2/ s, nitrilotriacetic acid(NTA) is industrial goods, ammonia concn 25%.
By the agent oil quality, than 0.10, the nitrilotriacetic acid(NTA) amount is 1.2 times of preparation decalcifying agents of calcium metal mole number in crude oil, and emulsion splitter FC-9301 adds wherein, concentration 0.03%.Under constantly stirring, adjust decalcifying agent pH to 10.0 with ammoniacal liquor, nitrilotriacetic acid(NTA) all dissolves, and obtains decalcifying agent solution.Agent oil is mixed into electrodesalting and electrodehydrating instrument effect 30 minutes at 80 ℃, is purified oil, and by analysis, its calcium contents is 9.0ppm, decalcification rate 91.1%.
Claims (4)
1. a crude oil complexing decalcification method, is characterized in that, at first nitrilotriacetic acid(NTA) is placed in to water and constantly stirs, Xiang Shuizhong drips gradually or stream adds ammonia solution, all dissolves to nitrilotriacetic acid(NTA), obtains decalcifying agent solution, by this liquid with crude oil and emulsion splitter, fully mix, emulsification, oily water separation after breakdown of emulsion;
The consumption of described nitrilotriacetic acid(NTA) is 0.9～5.0 times of calcium metal mole number in crude oil;
Described crude oil and decalcifying agent agent oil quality ratio are 0.03～0.15;
Described emulsion splitter add-on accounts for 20～50ppm of crude quality.
2. a kind of crude oil complexing decalcification method according to claim 1, is characterized in that, the pH value of described decalcifying agent solution is between 9.0～10.0.
3. a kind of crude oil complexing decalcification method according to claim 1, is characterized in that, the consumption of described nitrilotriacetic acid(NTA) is 1.0～2.0 times of calcium metal mole number in crude oil.
4. a kind of crude oil complexing decalcification method according to claim 1, is characterized in that, the operative temperature of described crude oil and decalcifying agent, and based on crude viscosity and determining, be greater than 40mm for 100 ℃ of kinematic viscosity
2the crude oil of/s, operative temperature is at 100 ℃～160 ℃; Be less than 40mm for 100 ℃ of kinematic viscosity
2the crude oil of/s, operative temperature is in normal temperature～100 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210168418.4A CN103450925B (en) | 2012-05-28 | 2012-05-28 | Crude oil complexing decalcification method |
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| CN201210168418.4A CN103450925B (en) | 2012-05-28 | 2012-05-28 | Crude oil complexing decalcification method |
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| CN103450925A true CN103450925A (en) | 2013-12-18 |
| CN103450925B CN103450925B (en) | 2015-02-25 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110068049A1 (en) * | 2009-09-21 | 2011-03-24 | Garcia Iii Juan M | Method for removing metals and amines from crude oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110068049A1 (en) * | 2009-09-21 | 2011-03-24 | Garcia Iii Juan M | Method for removing metals and amines from crude oil |
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