CN103450925B - Crude oil complexing decalcification method - Google Patents
Crude oil complexing decalcification method Download PDFInfo
- Publication number
- CN103450925B CN103450925B CN201210168418.4A CN201210168418A CN103450925B CN 103450925 B CN103450925 B CN 103450925B CN 201210168418 A CN201210168418 A CN 201210168418A CN 103450925 B CN103450925 B CN 103450925B
- Authority
- CN
- China
- Prior art keywords
- crude oil
- nitrilotriacetic acid
- nta
- calcium
- crude
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 a kind of method utilizing chemical agent to carry out crude oil decalcifying.
Background technology
Calcium metal in crude oil is processed with considerable influence to crude oil, and in petrochemical industry, its removing sulfuldioxide is representative in demetalization 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 kind of technology utilizes petroleum acid calcium principle in the displacement of strong acid in organic or inorganic crude oil 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, there is corrosive nature to industrial equipments, 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 aqueous phase and reach decalcification object, this method is comparatively friendly with equipment to environment, weak point is that consumption of chemical agent is large, the throw out produced is reacted for decalcification need with special separating device process.
Crude oil chelating decalcification method also claims complexing decalcification method, crude oil decalcifying technology as disclosed in CN8610728A, CN1036981A, CN87105863 etc., it adopts the aminocarboxylic acid, di-carboxylic acid, hydroxycarboxylic acid etc. that can generate water soluble complex with the Ca in crude oil to carry out crude oil decalcifying.The organic acid of the functional groups such as existing complexing decalcifying agent is generally containing carboxyl, hydroxyl, 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 object 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: first nitrilotriacetic acid(NTA) is placed in water and constantly stirs, Xiang Shuizhong drips gradually or stream adds ammonia solution, all dissolve to nitrilotriacetic acid(NTA), obtain decalcifying agent solution, this liquid is fully mixed with crude oil and emulsion splitter, emulsification, oily water separation after breakdown of emulsion.
In the present invention, nitrilotriacetic acid(NTA) and ammonia effect generate nitrilotriacetic acid(NTA) ammonium salt, and the pH value of its solution is between 9.0 ~ 10.0, and be a kind of excellent calcium ion complexing agent, meanwhile, this solution is corrosion-free to hardware, and 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 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, is greater than 40mm for 100 DEG C of kinematic viscosity
2the crude oil of/s, operative temperature is generally at 100 DEG C ~ 160 DEG C; 40mm is less than for 100 DEG C of kinematic viscosity
2the crude oil of/s, operative temperature is generally in normal temperature ~ 100 DEG C.
Emulsion splitter is that this area is general, and based on crude kind is screened, and effect promotes oily water separation, and its add-on generally accounts for 20 ~ 50ppm of crude quality.Emulsion splitter joins in decalcifying agent solution in advance, enters crude oil by decalcifying agent solution.
The method of the invention can remove the calcium of in crude oil more than 90%, does not produce secondary metals pollute de-rear crude oil, 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 decalcification rate is high.
Embodiment
With embodiment, the present invention is further described below.
Embodiment 1:
Experiment oil is Kelamayi Jiu Qu crude oil, and calcium contents is 220ppm, and its 100 DEG C of kinematic viscosity are 54mm
2/ s, nitrilotriacetic acid(NTA) is industrial goods, ammonia concn 25%.
By agent oil quality than 0.05, nitrilotriacetic acid(NTA) amount is calcium metal mole number 1.8 times preparation decalcifying agent in crude oil, and emulsion splitter FC-9301 adds wherein, concentration 0.1%.Under constantly stirring, adjust decalcifying agent solution 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 DEG C, and be purified oil, by analysis, its calcium contents is 12.5ppm, decalcification rate 94.3%.
Embodiment 2:
Experiment oil is Kelamayi Jiu Qu and the western commingled crude of stone, and calcium contents is its 100 DEG C of kinematic viscosity of 102ppm is 12mm
2/ s, nitrilotriacetic acid(NTA) is industrial goods, ammonia concn 25%.
By agent oil quality than 0.10, nitrilotriacetic acid(NTA) amount is calcium metal mole number 1.2 times preparation decalcifying agent in crude oil, and emulsion splitter FC-9301 adds wherein, concentration 0.03%.Under constantly stirring, adjust decalcifying agent solution 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 DEG C, and be purified oil, by analysis, its calcium contents is 9.0ppm, decalcification rate 91.1%.
Claims (2)
1. a crude oil complexing decalcification method, is characterized in that, first nitrilotriacetic acid(NTA) is placed in water and constantly stirs, Xiang Shuizhong drips gradually or stream adds ammonia solution, all dissolves to nitrilotriacetic acid(NTA), obtains decalcifying agent solution, this liquid is fully mixed with crude oil and emulsion splitter, 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;
The pH value of described decalcifying agent solution is between 9.0 ~ 10.0;
Described crude oil and the operative temperature of decalcifying agent, based on crude viscosity and determining, is greater than 40mm for 100 DEG C of kinematic viscosity
2the crude oil of/s, operative temperature is at 100 DEG C ~ 160 DEG C; 40mm is less than for 100 DEG C of kinematic viscosity
2the crude oil of/s, operative temperature is in normal temperature ~ 100 DEG C.
2. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168418.4A CN103450925B (en) | 2012-05-28 | 2012-05-28 | Crude oil complexing decalcification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168418.4A CN103450925B (en) | 2012-05-28 | 2012-05-28 | Crude oil complexing decalcification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103450925A CN103450925A (en) | 2013-12-18 |
| CN103450925B true CN103450925B (en) | 2015-02-25 |
Family
ID=49733769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210168418.4A Active CN103450925B (en) | 2012-05-28 | 2012-05-28 | Crude oil complexing decalcification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103450925B (en) |
Citations (1)
| 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 |
-
2012
- 2012-05-28 CN CN201210168418.4A patent/CN103450925B/en active Active
Patent Citations (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103450925A (en) | 2013-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5550167B2 (en) | Metal and amine removal promoting additives in refined desalting | |
| EP2989176B1 (en) | Method for controlling scale formation, using an allylsulfonate-styrene sulfonate polymer | |
| CN116082183A (en) | Multi-charged ionic compounds derived from polyamines, compositions thereof and use thereof as reverse demulsifiers for oil and gas operations | |
| JP2013505350A (en) | Improved method for removing metals and amines from crude oil | |
| CN103215064A (en) | Method for removing metal in high-acid heavy crude oil | |
| EP2601277A2 (en) | Method of removing multi-valent metals from crude oil | |
| CN103450925B (en) | Crude oil complexing decalcification method | |
| AU2014415242B2 (en) | Process for removing metal naphthenate from crude hydrocarbon mixtures | |
| CN103571523B (en) | Crude oil complex decalcifying agent composition and application thereof | |
| CN102220162B (en) | Method for reducing corrosivity of crude oil | |
| CN100386409C (en) | Chemical precipitation method for hydrocarbon decalcification | |
| WO2017039483A1 (en) | Wastewater cleaning agent and preparation method thereof | |
| CN102505122A (en) | Glauberite pipeline scale descaling agent and application thereof | |
| Chen et al. | Selective partition of potassium chloride and ammonium chloride by aqueous two-phase systems | |
| CN102260524B (en) | Chemical precipitation method for removing calcium from crude oil | |
| CN1521236A (en) | Method for removing metal from hydrocarbon oil using copolymers or its salts containing acrylic acid and sulfonic acid | |
| CN1431276A (en) | Method for removing metal from hydrocarbon oil by using inorganic acid | |
| CN102337150B (en) | Technical process and apparatus used in crude oil chemical decalcification | |
| EP2504407B1 (en) | Compositions and methods for inhibiting naphthenate solids formation from liquid hydrocarbons | |
| CN104059689A (en) | Oil product dechlorination method | |
| CN1323138C (en) | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid | |
| CN106381166A (en) | Method for decalcifying crude oil by ketonic acid | |
| CN101294101A (en) | Method for removing metal and petroleum acid from peracid primary oil | |
| US20130306522A1 (en) | Use of acid buffers as metal and amine removal aids | |
| CN102485838A (en) | Crude oil decalcifying agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |