CN1054261A - From hydrocarbon feed, remove metal with recombiner - Google Patents
From hydrocarbon feed, remove metal with recombiner Download PDFInfo
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- CN1054261A CN1054261A CN 91100633 CN91100633A CN1054261A CN 1054261 A CN1054261 A CN 1054261A CN 91100633 CN91100633 CN 91100633 CN 91100633 A CN91100633 A CN 91100633A CN 1054261 A CN1054261 A CN 1054261A
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Abstract
From hydrocarbon feed, remove metal with recombiner, especially efficiently remove sodium, calcium, magnesium, iron.The removal metal combinations that this explanation provides comprises precipitation agent, emulsion splitter and solid wetting agent.This method comprises two steps: the aqueous solution of hydrocarbon feed and recombiner carries out liquid-liquid in mixing tank mixes; Demetallated hydrocarbon feed carries out liquid-liquid separation with the water that comprises indissoluble throw out particulate under electric field action.Thereby slowed down poisoning of catalyst in the refining process, refinery's pipe laying and production unit fouling and etching problem can also improve the petroleum products quality simultaneously.Utilize refinery's electric desalting apparatus, desalinating process is optimized processing, and add recombiner, just can from hydrocarbon feed, efficiently remove sodium, calcium, magnesium and iron.
Description
The present invention relates to a kind of method that from the hydrocarbon feed that contains metal, efficiently removes sodium, calcium, magnesium and iron with recombiner.
As everyone knows, metals such as the calcium that contains in the hydrocarbon feed, magnesium, iron can not separate it from raw material with conventional desalting method, and they can cause the rapid catalyst deactivation in the hydrogenation technique process, for how to remove them from hydrocarbon feed just obtain paying attention to recently.Existing patent all is to adopt the chelating method, removes metal with different sequestrants from hydrocarbon feed, and in U.S. Pat 3,052, Lerner uses a kind of pyrrolidone-alcohol mixture that the metallic impurity in the crude oil are removed in 627; US3,167, the condensed polycyclic aromatic compound that Payne uses a kind of preferable C/H ratio and preferred molecular weight to be commonly referred to bituminous cement in 500 removes metal efficient from oil very high, but all to use dilution with toluene earlier for crude oil and heavier fraction oil, amount of chelant is bigger simultaneously, cost an arm and a leg, be not suitable for industrialization.
For overcome above-mentioned from crude oil the deficiency of process for demetalizating, from hydrocarbon feed, efficiently remove sodium, calcium, magnesium, the present invention adopts the comprehensive action of precipitation agent, emulsion splitter and solid wetting agent, has not only reached good effect and has helped industrialization.
Compound demetalizate agent provided by the present invention can efficiently remove sodium, calcium, magnesium from hydrocarbon feed.Its compound demetalizate agent comprises precipitation agent, emulsion splitter and solid wetting agent.After the precipitation agent aqueous solution and hydrocarbon feed mix,, be suspended in aqueous phase, from hydrocarbon feed, remove, reach the purpose that from hydrocarbon feed, removes metal with water with hydrocarbon feed institute metal ion formation insoluble solid precipitation particulate.Emulsion splitter impels oily water separation in order to destroy the emulsion that hydrocarbon feed and water form in mobile or mixing process.Emulsion splitter will be selected according to hydrocarbon feed of different nature, when single emulsion splitter does not reach the demulsification of expection, select composite demulsifying agent for use; The effect of solid wetting agent is to remove the oil film on solid impurity surface, makes it and water-wet, and the easier water that enters especially more is necessary to add the solid wetting agent for heavy crude.For demetalization from crude oil, must comprise emulsion splitter and precipitation agent in the compound demetalizate agent, have only heavy crude just need add the solid wetting agent.In the recombiner, the kind of emulsion splitter and consumption will conscientiously be chosen definite to concrete crude oil.The content of precipitated metal ion is determined in the consumption based on crude of precipitation agent.The solid wetting agent is necessary to some heavy crude.Compound demetalizate agent can be mixed in proportion the back to be mixed with crude oil, also can add respectively simultaneously in proportion and the crude oil mixing.
Exemplary flow of the present invention is seen accompanying drawing 1.The aqueous solution (2) that is heated to 30～150 ℃ hydrocarbon feed (1) and contains the compound demetalizate agent of being made up of precipitation agent, emulsion splitter and solid wetting agent enters mixing tank (3) simultaneously; Mixing tank can be a mixing valve, static mixer or electrostatic dispersion device.Hydrocarbon feed carries out in mixing tank (3) fully evenly with compound demetalizate agent, liquid-liquid mixes fully, make and the effect of porphyrins by compound demetalizate agent of the organic salt of metal inorganic salt in the hydrocarbon feed, metal and metal generate the insoluble throw out.In electrical desalter (4), electrical desalter can be selected vertical tank for use, horizontal tank or spherical tank, under strength of electric field 300～5000v/cm condition, both available DC electric field also can adopt alternating-electric field, the aqueous phase separation of the insoluble solid sediment micro mist of the demetallated hydrocarbon feed and the generation that suspending, demetallated hydrocarbon feed (5) causes follow-up refining plant from the electrical desalter top, and the water of containing metal solid sediment is discharged from the electrical desalter bottom.
Characteristics of the present invention are that the aqueous solution (precipitation agent, emulsion splitter and solid wetting agent) and the hydrocarbon feed with recombiner carries out liquid-liquid blend in mixing tank, and mixing tank has mixing valve, static mixer and electrostatic dispersion device etc.Liquid-liquid mixing reaches fully evenly, thorough mixing, enter in the electrical desalter, under electrostatic field, make and contain the water that precipitates particulate and separate with hydrocarbon feed, the electric field of hydrocarbon water sepn both can be that DC electric field also can be an alternating-electric field, and used strength of electric field is 300～5000v/cm, utilizes the effect of static flocking settling, quicken the sepn process of hydrocarbon feed and water, from hydrocarbon feed, efficiently remove sodium, calcium, magnesium and iron.The effect of the precipitation agent in the above-mentioned recombiner be to make it with hydrocarbon feed in metal ion, particularly oil soluble metal compound in metal ion generate the insoluble precipitation and enter water, get rid of with water.Precipitation agent was both a kind of, two or more precipitation agent is composite again, precipitation agent be those can be removed metal ion and generate the sedimentary compound of indissoluble, for example: phosphoric acid and its esters, hydrosulphuric acid and its esters etc., preferable precipitation agent is an ammonium phosphate, and the add-on of precipitation agent is 0.5～10 times of metal integral molar quantity in the hydrocarbon feed, and preferable add-on is 1～4 times.Emulsion splitter and composite demulsifying agent want based on crude character selected, all will conscientiously evaluate every kind of crude oil.When single emulsion splitter does not reach effect, adopt composite demulsifying agent, the effect of emulsion splitter is to destroy hydrocarbon feed and water formed emulsion when flowing or mixing, and impels oily water separation.Its add-on is generally the 1-100ppm of hydrocarbon feed weight.The effect of solid wetting agent is to remove the oil film on some solid impurity surface, make it and water-wet, the easier water that enters, the solid wetting agent is primarily aimed at some solid heavy crude and uses, usually adopt vitriol and oxygen hydroxyl phenol, in the vitriol, concerning crude oil electric desalting, preferably ammonium sulfate, add-on is the 1-30ppm of hydrocarbon feed weight.
Recombiner is very high to the decreasing ratio of metal in the hydrocarbon feed, and the decreasing ratio of sodium, calcium, magnesium is near 100%, and the decreasing ratio of iron is 90%, simultaneously to nickel, vanadium, copper, also certain removal effect arranged.Utilize electric desalting apparatus, the demetalization that can carry out hydrocarbon feed after the desalinating process optimization is handled, be applicable to the demetalization process of various hydrocarbon ils and crude oil, the hydrocarbon feed that removes metal can alleviate the poisoning of catalyst of heavy oil fluid catalytic cracking and hydrogenation and the fouling and the etching problem of process furnace, cold exchange device and pipeline in the follow-up course of processing, improve the quality of petroleum products simultaneously.
Accompanying drawing and explanation thereof: accompanying drawing 1 is a block diagram of the present invention.
The 1-hydrocarbon feed
The 2-recombiner aqueous solution
3-liquid-liquid mixer
The 4-electrical desalter
5-demetalization hydrocarbon feed
6-discharges the sedimentary water of containing metal
7-refined hydrocarbon jar
LIAOHE CRUDE, contain sodium 9.3ppm, calcium 33.7ppm, magnesium 10.6ppm, iron 20.2ppm, vanadium 1.6ppm, nickel 41.9ppm before the demetalization, copper 8.1ppm adds ammonium phosphate 200ppm, emulsion splitter AP221 20ppm, add solid wetting agent ammonium sulfate 5ppm, mix the back under 135 ℃, added electric field 600v/cm, 10 minutes.Get oil analysis after the demetalization: remove sodium, calcium is 100%, magnesium is 90.8%, and iron is 90%, and content of vanadium is 0.44ppm, and decreasing ratio 72.5%, nickel content are 33.1ppm, decreasing ratio 21%, and copper content 2.4ppm, decreasing ratio are 70.4%.
Prolong crude oil, contain sodium 232.3ppm before the demetalization, calcic 209.7ppm, magnesium 7.5ppm, iron 18.1ppm, nickel 0.7ppm, copper 3.1ppm adds ammonium phosphate 250ppm, emulsion splitter BP2040 18ppm, at 100 ℃, added electric field 700v/cm, 10 minutes, get the oil analysis sodium after the demetalization, the decreasing ratio of magnesium is 100%, calcium 99.1%, iron level is 1.8ppm, decreasing ratio 90%, nickeliferous 0.6ppm, decreasing ratio 14.3%, copper content 2.0ppm, decreasing ratio 32.3%.
Claims (16)
1, a kind of method that makes hydrocarbon feed remove metal: it comprises
The recombiner of a, use is precipitation agent, emulsion splitter and solid wetting agent composite a dose.
B, hydrocarbon feed and the described recombiner aqueous solution carry out liquid-liquid simultaneously in mixing tank mixes.
The water of c, demetalization hydrocarbon feed and containing metal solid sediment quickens flocking settling under electric field action, carry out liquid-liquid separation, efficiently removes metals such as sodium, calcium, magnesium, iron.
2, method according to claim 1, wherein the metal that need remove from described hydrocarbon feed comprises the metal of I family.
3, method according to claim 2, wherein said metal is a sodium.
4, method according to claim 1 wherein needs comprise from the metal that described hydrocarbon feed removes the metal of II family.
5, according to the method for claim 4, wherein said metal is calcium and magnesium.
6, method according to claim 1, wherein said precipitation agent are phosphoric acid and its esters.
7, method according to claim 6, wherein said preferable precipitation agent is an ammonium phosphate.
8, according to the method for claim 7, the add-on of wherein said precipitation agent is 0.5～10 times of metal integral molar quantity in the hydrocarbon feed.
9, method according to Claim 8, the preferable add-on of wherein said precipitation agent are 1～4 times of the total mole of metal in the hydrocarbon feed.
10, according to the process of claim 1 wherein that the hydrocarbon feed and the precipitation agent aqueous solution carry out fully evenly, liquid-liquid mixes fully in mixing tank.
11, according to the process of claim 1 wherein that described emulsion splitter add-on is 1～100ppm of hydrocarbon feed weight.
12, according to the process of claim 1 wherein that described solid wetting agent is vitriol and oxygen hydroxyl phenol.
13, according to the method for claim 12, wherein said preferable solid wetting agent is that the ammonium sulfate add-on is the 1-30ppm of hydrocarbon feed weight.
14, method according to claim 1, wherein said hydrocarbon feed heated before entering mixing tank.
15, method according to claim 14, the preferred temperature of wherein said hydrocarbon feed heating is 30～150 ℃.
16, method according to claim 1, the electric field of wherein said liquid-liquid separation can adopt DC electric field can adopt alternating-electric field again, and strength of electric field is 300～5000V/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100633 CN1028537C (en) | 1991-02-06 | 1991-02-06 | Removal of metals from hydrocarbon raw material with complexing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100633 CN1028537C (en) | 1991-02-06 | 1991-02-06 | Removal of metals from hydrocarbon raw material with complexing agent |
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| Publication Number | Publication Date |
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| CN1054261A true CN1054261A (en) | 1991-09-04 |
| CN1028537C CN1028537C (en) | 1995-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100633 Expired - Fee Related CN1028537C (en) | 1991-02-06 | 1991-02-06 | Removal of metals from hydrocarbon raw material with complexing agent |
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| CN (1) | CN1028537C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069683C (en) * | 1997-12-23 | 2001-08-15 | 中国石油化工总公司 | Method for demetal from masrolar D using compound containing sulfur and phosphorus |
| CN1078234C (en) * | 1998-08-18 | 2002-01-23 | 中国石油化工集团公司 | Compound decalcifying agent for hydrocarbon oil and its application |
| WO2005005579A1 (en) * | 2003-06-03 | 2005-01-20 | Karamay Jinshan Petrochemical Limited Company | A circular method for desalting the hydrocarbon oil |
| CN102485838A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Crude oil decalcifying agent |
| US9790438B2 (en) | 2009-09-21 | 2017-10-17 | Ecolab Usa Inc. | Method for removing metals and amines from crude oil |
| US9963642B2 (en) | 2002-08-30 | 2018-05-08 | Baker Petrolite LLC | Additives to enhance metal and amine removal in refinery desalting processes |
| CN108929714A (en) * | 2018-08-03 | 2018-12-04 | 李昕 | A kind of de-sodium agent of the Organic Sodium Salt suitable for crude oil |
| EP3431571A1 (en) * | 2017-07-21 | 2019-01-23 | Grupo Tradebe Medioambiente, S.L. | Method for treating heavy hydrocarbon residues containing calcium and other heavy metals and product obtained |
| CN111471485A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Method for removing sodium salt from hydrocarbon oil |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429325C (en) * | 2007-03-08 | 2008-10-29 | 北京化工大学 | Method of eliminating and reclaiming metal form petroleum |
-
1991
- 1991-02-06 CN CN 91100633 patent/CN1028537C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069683C (en) * | 1997-12-23 | 2001-08-15 | 中国石油化工总公司 | Method for demetal from masrolar D using compound containing sulfur and phosphorus |
| CN1078234C (en) * | 1998-08-18 | 2002-01-23 | 中国石油化工集团公司 | Compound decalcifying agent for hydrocarbon oil and its application |
| US9963642B2 (en) | 2002-08-30 | 2018-05-08 | Baker Petrolite LLC | Additives to enhance metal and amine removal in refinery desalting processes |
| WO2005005579A1 (en) * | 2003-06-03 | 2005-01-20 | Karamay Jinshan Petrochemical Limited Company | A circular method for desalting the hydrocarbon oil |
| US7455763B2 (en) | 2003-06-03 | 2008-11-25 | Karamay Jinshan Petrochemical Limited Company | Recycling process for demetalization of hydrocarbon oil |
| US9790438B2 (en) | 2009-09-21 | 2017-10-17 | Ecolab Usa Inc. | Method for removing metals and amines from crude oil |
| CN102485838A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Crude oil decalcifying agent |
| EP3431571A1 (en) * | 2017-07-21 | 2019-01-23 | Grupo Tradebe Medioambiente, S.L. | Method for treating heavy hydrocarbon residues containing calcium and other heavy metals and product obtained |
| CN108929714A (en) * | 2018-08-03 | 2018-12-04 | 李昕 | A kind of de-sodium agent of the Organic Sodium Salt suitable for crude oil |
| CN111471485A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Method for removing sodium salt from hydrocarbon oil |
| CN111471485B (en) * | 2019-01-23 | 2021-12-17 | 中国石油化工股份有限公司 | Method for removing sodium salt from hydrocarbon oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1028537C (en) | 1995-05-24 |
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