CN1076473A - From hydrocarbon feed, remove metallic impurity with inorganic phosphorated chelating agent - Google Patents
From hydrocarbon feed, remove metallic impurity with inorganic phosphorated chelating agent Download PDFInfo
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- CN1076473A CN1076473A CN 92113219 CN92113219A CN1076473A CN 1076473 A CN1076473 A CN 1076473A CN 92113219 CN92113219 CN 92113219 CN 92113219 A CN92113219 A CN 92113219A CN 1076473 A CN1076473 A CN 1076473A
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Abstract
From hydrocarbon feed, remove metallic impurity with inorganic phosphorated chelating agent, particularly efficiently remove calcium, magnesium, iron.Tripoly phosphate sodium STPP that the present invention uses and Sodium hexametaphosphate 99 are to calcium in the hydrocarbon ils, magnesium, the highest decreasing ratio of iron all can reach more than 80%, during the crude oil demetalization experiment carried out at crude electric desalter with this sequestrant, can make the crude electric desalter electric current reduce by 50%, power consumption descends 40%, simultaneously, the residual oil catalytic cracking product is distributed to improve, the gasoline average yield improves 1.8%, also can make metal adsorption amount reduction on the catalyzer, wherein sodium reduces by 15～25%, and calcium reduces by 20～30%, iron reduces by 35～45%, magnesium reduces by 25～35%, nickel reduces by 20～30%, vanadium reduces by 30～35%.
Description
The present invention relates to a kind ofly from hydrocarbon feed, remove the method for metallic impurity, specially refer to polyphosphoric acid and salt thereof and from hydrocarbon feed, remove calcium, magnesium, iron etc. with inorganic phosphorated chelating agent.
Metallic impurity in the hydrocarbon oil crude material have serious harm to the use of hydrocarbon ils and the following process of hydrocarbon ils.The hydrocarbon ils that contains metallic impurity is done the fuel time spent, produces fouling easily in roasting kiln, and influence is conducted heat, and can cause thermal etching.When these hydrocarbon ils were made catalytic cracking and hydrogenating materials, metallic impurity such as sodium, calcium, magnesium, iron, nickel, vanadium can cause poisoning of catalyst incrustation, and catalyst activity is reduced, even influenced the normal operation of device.During as coking raw material, then increase the ash content in the refinery coke, reduce the grade of refinery coke.
Present crude oil electric desalting technology can only remove most of sodium salt, inorganic chlorine, moisture and the suspended solid in the crude oil.Naphthenate in the hydrocarbon ils, phenates and porphyrin class inner complex are insoluble in water, can not remove effectively with common desalting method.In order to reduce the content of metals in hydrocarbon oil impurity, the oil refining worker has made number of research projects, for example, Lerner uses a kind of pyrrolidone-alcohol mixture that the metallic impurity in the crude oil are removed in the U.S. Pat 3052627, in the U.S. Pat 3167500 Payne use a kind of have preferable C H than and the preferred molecular weight fused-ring aromatic compound that is commonly referred to bituminous cement to remove metal efficient from hydrocarbon ils very high.Among the US3153623, people such as Eidib select the commercially available organic compound of some high dielectric strengths, and it is added in the technological process to promote the electric precipitating process of metal.Among the US4439345, Duke discloses and has a kind ofly removed metal so that the method for its breakdown of emulsion with carboxylic acid from the intermediate phase emulsion that strengthens petroleum products.Among the Chinese patent CN1036981A, John G Reynolds has proposed to remove from hydrocarbon feed with di-carboxylic acid the method for metal now.CN37105863A has announced a kind of with ethylenediamine tetraacetic acid (EDTA) and salt demetallated method from hydrocarbon ils thereof.Above hydrocarbon ils removes the method for metallic impurity, not only cost height, and complex process.
The purpose of this invention is to provide a kind of hydrocarbon oil metal removal agent, this metal remover should possess removal efficiency height, characteristics such as cheap, easy to use simultaneously, for industrial application creates conditions.
Inorganic phosphorated chelating agent provided by the present invention, particularly tripoly phosphate sodium STPP, Sodium hexametaphosphate 99 etc. can efficiently remove metallic impurity such as calcium in the hydrocarbon feed, magnesium, iron.The sequestrant that is provided among pending hydrocarbon ils and the present invention, polar solvent and emulsion splitter are through thorough mixing, metallic impurity in sequestrant and the hydrocarbon ils form complex compound and are dissolved in the solvent phase, under the acting in conjunction of certain temperature, electric-force gradient, emulsion splitter, solvent phase is separated from hydrocarbon ils, thereby metallic impurity are removed from hydrocarbon ils, and wherein said sequestrant is polyphosphoric acid, polyphosphoric acid salt and their mixture.Simultaneously, these sequestrants also can use with other compound with network and effect or precipitating action, as ethylenediamine tetraacetic acid (EDTA) and salt and phosphoric acid salt etc.The consumption of sequestrant is generally 10～1000ppm, and optimum amount is 50～200ppm.Used polar solvent comprises that water, pure and mild other of lower aliphatic are insoluble to the compound of hydrocarbon ils among the present invention, and wherein best solvent is water, methyl alcohol, ethanol, propyl alcohol, Virahol etc.The consumption of solvent is generally the 1-50%(wt of pending hydrocarbon ils), optimum amount is 3-20%.Being used for the demetallated emulsion splitter model of hydrocarbon ils, is selected by the breakdown of emulsion test according to concrete hydrocarbon ils kind, and the hydrocarbon ils demetalization is carried out between hydrocarbon ils condensation point to 200 ℃ usually, and best temperature range is 90-150 ℃.Electric-force gradient generally is controlled between 500～1500v/cm, and best electric-force gradient is 800～1000v/cm.
Method of the present invention can make the decreasing ratio of calcium in the hydrocarbon ils, magnesium, iron reach more than 90%.From the commerical test of having finished, when crude oil demetalization and desalination are carried out simultaneously, the used sequestrant of the present invention can make the crude oil electric desalting electric current reduce by 50%, this has not only reduced the energy consumption of crude oil electric desalting, simultaneously, the design capacity of electric desalting apparatus electrical equipment is reduced, reduce equipment manufacturing cost.Because cracking has katalysis to used sequestrant to hydrocarbon feed among the present invention, particularly it can form with catalyzer toxin such as nickel, vanadium has better active catalyzer to cracking, therefore, catalytic cracking has promoter action to a small amount of metal remover contained in the hydrocarbon oil crude material after the processing to hydrocarbon feed, the product that it can improve the hydrocarbon feed catalytic cracking distributes, and improves yield of light oil.Test-results shows that it can make the catalytically cracked gasoline yield improve 0.5～5%.In addition, hydrocarbon ils is after the inventive method demetalization, the metal that has adsorbed on the hydrocarbon feed catalytic cracking catalyst is partly removed, and wherein sodium reduces 15-25%, calcium minimizing 20～30%, iron minimizing 35-45%, magnesium minimizing 25-35%, nickel minimizing 20-30%, and vanadium reduces 30-35%.So both catalyst activity can be improved, also catalyst consumption can be reduced.The present invention is applicable to the demetalization processing of crude oil and fraction oil and other all hydrocarbon raw materials.
The following examples are to further specify of the present invention, rather than limit its scope of application.
Embodiment 1
Boiling range is 230～400 ℃ a hydrocarbon feed, wherein contain sodium 1.5ppm, calcium 1.7ppm, magnesium 0.11ppm, iron 27ppm, nickel 12ppm, vanadium 0.9ppm, the water of adding 5%, 15ppmN-17 emulsion splitter and 130ppm Sodium hexametaphosphate 99, behind the thorough mixing, carry out the hydrocarbon ils demetalization and handle under 100 ℃, 1000v/cm electric field action, the metal content that takes off in the hydrocarbon ils of back is respectively sodium 0.2ppm, calcium 0.2ppm, magnesium 0.05ppm, iron 2.4ppm.
Embodiment 2
Contain sodium 29ppm, calcium 23ppm, magnesium 7ppm, iron 12ppm in the crude oil, add 5% ethylene glycol and 1% water, add 100ppm compound complex agent (wherein tripoly phosphate sodium STPP 80%, EDTA20%) and PR7525 emulsion splitter 30ppm simultaneously, after filling mixing, under 130 ℃, 700v/cm electric field action, carry out the crude oil demetalization and handle.Take off back crude oil and contain sodium 1.9ppm, calcium 1.7ppm, magnesium 0.9ppm, iron 3.2ppm.
Embodiment 3
On the industrial electro desalting plant, add 5% water, the 20ppm emulsion splitter is at 120 ℃, (90ppm Sodium hexametaphosphate 99) carries out huge port crude oil demetalization under the 900v/cm electric-force gradient condition, and crude oil contains sodium 17.2ppm, calcium 15ppm, magnesium 0.5ppm, iron 10ppm, nickel 28.5ppm, vanadium 0.3ppm before taking off.Take off back crude oil and contain sodium 1.1ppm, calcium 2.3ppm, magnesium 0.2ppm, iron content 2.2ppm, nickel 27.0ppm, vanadium 0.2ppm.Adding the preceding electric desalting apparatus electric current of agent is 90A, add in the agent process, electric current is reduced to 12A, power consumption is from 0.6 degree, ton is reduced to 0.1 degree, when the long residuum after this crude oil of ton distills through atmospheric tower was used for catalytic cracking, the metal content on the catalytic cracking catalyst all descended to some extent, and rate of descent is respectively sodium 15～25%, calcium 20～30%, iron 35～45%, magnesium 25～35%, nickel 20～30%, vanadium 30～35%.In addition, the residual oil catalytic cracking product distributes and improves, and the gasoline average yield improves 1.8%.
Claims (5)
1, comprise with inorganic phosphorated chelating agent demetal process process from hydrocarbon feed:
A, hydrocarbon ils and inorganic phosphorated chelating agent, polar solvent and emulsion splitter are through thorough mixing;
B, the polar solvent that purifies hydrocarbon ils and containing metal impurity separate under electric field and emulsion splitter effect.
2, according to claim 1, wherein said inorganic phosphorated chelating agent is polyphosphoric acid and salt thereof.
3, according to claim 2, wherein said best inorganic phosphorated chelating agent is tripoly phosphate sodium STPP and Sodium hexametaphosphate 99.
4, according to claim 1, the consumption of wherein said inorganic phosphorated chelating agent is 10～1000ppm.
5, according to claim 4, the optimum amount of inorganic phosphorated chelating agent is 50～200ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113219 CN1028648C (en) | 1992-11-25 | 1992-11-25 | Removing metal impurities from hydrocarbon materials by inorganic phosphorated chelating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113219 CN1028648C (en) | 1992-11-25 | 1992-11-25 | Removing metal impurities from hydrocarbon materials by inorganic phosphorated chelating agent |
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| Publication Number | Publication Date |
|---|---|
| CN1076473A true CN1076473A (en) | 1993-09-22 |
| CN1028648C CN1028648C (en) | 1995-05-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92113219 Expired - Fee Related CN1028648C (en) | 1992-11-25 | 1992-11-25 | Removing metal impurities from hydrocarbon materials by inorganic phosphorated chelating agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106464A1 (en) * | 2003-06-03 | 2004-12-09 | Karamay Jinshan Petrochemical Limited Company | A demetalizing agent for hydrocarbon oil and its preparation and use |
| CN103146417A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Composite demetalization agent and preparation method thereof |
| CN103146421A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Method for removing metals from crude oil |
| CN103194257A (en) * | 2013-04-18 | 2013-07-10 | 中国人民解放军空军油料研究所 | Method for removing trace metal from coal-based direct liquefied fraction oil |
| CN108707470A (en) * | 2018-06-14 | 2018-10-26 | 陕西省石油化工研究设计院 | A kind of oils metal remover and the preparation method and application thereof |
-
1992
- 1992-11-25 CN CN 92113219 patent/CN1028648C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106464A1 (en) * | 2003-06-03 | 2004-12-09 | Karamay Jinshan Petrochemical Limited Company | A demetalizing agent for hydrocarbon oil and its preparation and use |
| CN103146417A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Composite demetalization agent and preparation method thereof |
| CN103146421A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Method for removing metals from crude oil |
| CN103146417B (en) * | 2011-12-07 | 2015-02-18 | 中国石油化工股份有限公司 | Composite demetalization agent and preparation method thereof |
| CN103146421B (en) * | 2011-12-07 | 2016-03-16 | 中国石油化工股份有限公司 | A kind of crude oil process for demetalizating |
| CN103194257A (en) * | 2013-04-18 | 2013-07-10 | 中国人民解放军空军油料研究所 | Method for removing trace metal from coal-based direct liquefied fraction oil |
| CN108707470A (en) * | 2018-06-14 | 2018-10-26 | 陕西省石油化工研究设计院 | A kind of oils metal remover and the preparation method and application thereof |
| CN108707470B (en) * | 2018-06-14 | 2021-05-04 | 陕西省石油化工研究设计院 | Oil demetallization agent and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1028648C (en) | 1995-05-31 |
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