CN102250640B - Method for removing nickel and vanadium from hydrocarbon oil - Google Patents
Method for removing nickel and vanadium from hydrocarbon oil Download PDFInfo
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- CN102250640B CN102250640B CN201010177792.1A CN201010177792A CN102250640B CN 102250640 B CN102250640 B CN 102250640B CN 201010177792 A CN201010177792 A CN 201010177792A CN 102250640 B CN102250640 B CN 102250640B
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Abstract
The invention relates to a method for removing nickel and vanadium from hydrocarbon oil. The method comprises the following steps: 1, the hydrocarbon oil is processed by ultrasonic waves at a temperature of 20-150 DEG C, and the viscosity of the hydrocarbon oil under the processing temperature is equal to or less than 100mm<2>/s; 2, the hydrocarbon oil which is processed by the ultrasonic waves is mixed with a demulsifier and water, and an oil phase is separated after demulsifying and dehydrating under the effect of an electric field; and 3, a demetallization agent is added in step 1 or step 2. The method provided by the present invention can effectively remove nickel and vanadium from the hydrocarbon oil.
Description
Technical field
The present invention relates to a kind of method that removes nickel and vanadium from hydrocarbon ils.
Background technology
Along with the continuous intensification of Oil extraction degree, oil property trends towards heaviness, in poor quality, and the metal content in part crude oil is generally higher, and particularly the content of nickel and vanadium is higher.With other metallic element, compare, nickel and vanadium are present in colloid, bituminous matter mainly with the form of porphyrin and non-porphyrin organic coordination compound greatly, are difficult to be removed by electric desalting apparatus.Nickel and vanadium are very large to crude oil secondary processing process harm, the serious consequences such as catalytic cracking catalyst is poisoning as caused, the catalyst deactivation in heavy-oil hydrogenation cracking process and bed obstruction.Vanadium is larger to the harm of oil fuel, as vanadium can form (Na when burning
2o)
xv
2o
5low melting point molten thing altogether, bring out hardware thermal etching, cause fuel oil boiler tube burn into gas turbine blades corrosion etc.In sum, removing nickel and vanadium in crude oil has very important significance.
By means such as hydrotreatment, coking and solvent deasphaltings, the nickel in heavy oil, vanadium can be removed or shifted, but the investment of these methods is large, cost is high.
Chinese patent application CN101381620A discloses a kind of process for demetalizating of oil product, the method, first by oil product preheating, after adding metal remover and water fully to mix, is carried out ul-trasonic irradiation, within finally standing 1 hour at 60-90 ℃, carry out oily water separation, metal in oil product is removed.The weak point of the method is nickel and the vanadium that is only applicable to remove in wax oil, is not suitable for the nickel and the vanadium that remove in crude oil, long residuum or vacuum residuum, and the content of nickel in wax oil and vanadium is conventionally lower.
Summary of the invention
The object of this invention is to provide a kind of method that removes nickel and vanadium from hydrocarbon ils, the method combines chemical action, ul-trasonic irradiation and electric field action, can effective elimination crude oil, nickel and vanadium in long residuum or vacuum residuum.
A method that removes nickel and vanadium from hydrocarbon ils, comprising:
(1), between 20～150 ℃, use ultrasonication hydrocarbon ils, the viscosity≤100mm of described hydrocarbon ils under treatment temp
2/ s;
(2) hydrocarbon ils after ultrasonication is mixed with emulsion splitter and water, under electric field action, after breaking emulsion and dewatering, isolate oil phase;
(3) in step (1) or step (2), add metal remover;
Wherein, described hydrocarbon ils is the mixture of component A or component A and B component; Component A is selected from one or more in crude oil, long residuum or vacuum residuum, and B component is selected from the petroleum fractions of boiling point between 100～350 ℃ or one or more in petroleum products.
The quality of hydrocarbon ils of take is benchmark, and the content of vanadium in hydrocarbon ils is preferably 5～1000ppm, more preferably 20～500ppm; Nickel content is preferably 2～500ppm, more preferably 5～250ppm.
Described petroleum fractions is kerosene or solar oil.
Described petroleum products is solvent oil.
In the present invention, metal remover is had no particular limits, can use the metal remover of this area routine, as being one or more in inorganic phosphate and salt thereof, organic phospho acid and salt thereof, sulfonic acid, halogenated carboxylic acid, cyanic acid and salt thereof, thiocyanic acid and salt thereof, isocyanic acid and salt thereof and isocyanic ester, one or more in following compounds preferably: phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, tetra-sodium, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, CH
3pO
3h
2, phosphoramidic acid, methylsulfonic acid, two methylsulfonic acids, Phenylsulfonic acid, naphthene sulfonic acid, methyl-sulfinic acid, trifluoroacetic acid, trichoroacetic acid(TCA) and tolylene diisocyanate.
The quality of hydrocarbon ils of take is benchmark, and the consumption of metal remover is preferably 100～10000 μ g/g, more preferably 500～3000 μ g/g.
In step (1), by the mode of ultrasonication hydrocarbon ils, can adopt the mode of intermittent action or the mode of continuous action, preferably intermittent action mode.
In step (1), be preferably 5～60min with the time of ultrasonication hydrocarbon ils, more preferably 10～30min; Amplitude is preferably 25～112 μ m, more preferably 75～100 μ m; Calibration is 15kHz～130kHz, more preferably 20kHz～40kHz.Ultrasonic wave in the present invention refers to that frequency is greater than the sound wave of 15kHz.
When adopting intermittent action mode, described " time of ultrasonication hydrocarbon ils " refers to the cumulative time of ul-trasonic irradiation.
The present invention has no particular limits emulsion splitter, can adopt the emulsion splitter of this area routine.
Those skilled in the art know the consumption of emulsion splitter and water and how under electric field action, to carry out breaking emulsion and dewatering.Generally, the quality of hydrocarbon ils of take is benchmark, and the consumption of emulsion splitter is 10～200 μ g/g, preferably 30～100 μ g/g; The quality of hydrocarbon ils of take is benchmark, and the consumption of water is 3%～20%, preferably 5%～10%; The temperature range of breaking emulsion and dewatering is 60～145 ℃, preferably 80～130 ℃; Electric-force gradient is 200～2000V/cm, is preferably 400～1000V/cm.
In preferred situation, the present invention by described hydrocarbon ils with after ultrasonication, utilize the electric desalting process of refinery to carry out breaking emulsion and dewatering, utilize the electric desalting apparatus of refinery and technology of electric de-salting to carry out breaking emulsion and dewatering.
Nickel in heavy hydrocarbon oil and vanadium are present in colloid, bituminous matter mainly with the form of porphyrin and non-porphyrin organic coordination compound greatly, are difficult to be removed by electric desalting apparatus.By means such as hydrotreatment, coking and solvent deasphaltings, the nickel in heavy hydrocarbon oil and vanadium can be removed or shifted, but the investment of these methods is large, cost is high.Prior art adds the wax oil of metal remover and water by ultrasonication, can remove nickel and vanadium in wax oil, but the method is during for the treatment of crude oil, long residuum or vacuum residuum, can cause serious emulsification, cannot effective elimination nickel and vanadium wherein, also cannot be for electric desalting process.Method provided by the invention combines chemical action, ul-trasonic irradiation and electric field action, can effectively remove nickel and vanadium in crude oil, long residuum or vacuum residuum.Method of the present invention has reaction conditions gentleness, easy to operate, low cost and other advantages, is easy to industrial application.
Embodiment
Further set forth by the following examples the present invention.VCX750 type Ultrasonic cell smash (the frequency 20kHz that the ultrasonoscope using in embodiment is produced for U.S. SONICS & MATERIALS company, peak power output 750W, probe base diameter 13mm, peak swing 124 μ m, can process sample 10～250ml, amplitude is adjustable and have amplitude automatic compensation function).Ultrasonic intensity changes by adjusting amplitude size to be realized.
Embodiment mono-
Oil density 0.86g/cm
3, viscosity (50 ℃) 8.484mm
2/ s, metal remover is phosphorous acid, emulsion splitter is NS-9800 (Nanjing petrochemical iy produced).
Scheme one, get 80g crude oil in beaker, add 2000 μ g/g metal removers, be placed in VCX750 type ultrasound reactor, at room temperature react 30min, adopt periodical operation (operation 2s stops 4s), amplitude 87 μ m, sample after reaction is poured in mixing tank, add 10g distilled water fully to mix with 20 μ g/g emulsion splitters, pack minute water bottle into and be placed in electrostatic field 30min and carry out oily water separation, 80 ℃ of temperature, strength of electric field 400V/cm, by the upper strata oil sample sampling analysis metallic nickel, the content of vanadium that obtain.
Scheme two, gets 80g crude oil in beaker, is placed in VCX750 type ultrasound reactor, at room temperature react 30min, adopt periodical operation (operation 2s stops 4s), amplitude 87 μ m, pour sample after reaction in mixing tank into, add 2000 μ g/g metal removers, 10g distilled water and 20 μ g/g emulsion splitters fully mix, and are then placed in electrostatic field 30min and carry out oily water separation, 80 ℃ of temperature, strength of electric field 400V/cm, by the upper strata oil sample sampling analysis metallic nickel, the content of vanadium that obtain.
Test-results is in Table 1.
Table 1
Embodiment bis-
Oil density 0.90g/cm
3, viscosity (80 ℃) 50.16mm
2/ s, belongs to low-sulfur paraffinic crude, and metal remover is hydroxy ethylene diphosphonic acid (HEDP), and emulsion splitter is 2635A (production of Shandong Bin Hua group).
Crude oil is preheated to 80 ℃ and carries out again ultrasonic response, electrostatic field treatment time 40min, 90 ℃ of temperature, strength of electric field 400V/cm, other conditions are with embodiment mono-, and test-results is in Table 2.
Table 2
Embodiment tri-
Oil density 0.96g/cm
3, viscosity (80 ℃) 48.56mm
2/ s, belongs to high-sulfur naphthenic base crude, and metal remover is methylsulfonic acid, and emulsion splitter is NS-2040 (Nanjing petrochemical iy produced).
Crude oil is preheated to 80 ℃ and carries out again ultrasonic response, electrostatic field treatment time 60min, 100 ℃ of temperature, strength of electric field 400V/cm, other conditions are with embodiment mono-, and test-results is in Table 3.
Table 3
Embodiment tetra-
Oil density 0.94g/cm
3, viscosity (80 ℃) 68.32mm
2/ s, belongs to high-sulfur intermediate base crude oil, and metal remover is trichoroacetic acid(TCA), and emulsion splitter is BSK-609 (production of Shandong Bin Hua group).
Crude oil is preheated to 80 ℃ and carries out again ultrasonic response, electrostatic field treatment time 60min, 100 ℃ of temperature, strength of electric field 400V/cm, other conditions are with embodiment mono-, and test-results is in Table 4.
Table 4
| Scheme two | 20.52 | 96.2 | 37.9 |
Embodiment five
Long residuum density 0.97g/cm
3, viscosity (80 ℃) 316.7mm
2/ s, metal remover is tolylene diisocyanate, emulsion splitter is oil soluble NS-80 (Nanjing petrochemical iy produced).
This long residuum colloid, asphalt content are high, and viscosity is large, before test with 200
#solvent oil evenly mixes in mass ratio at 1: 1, then under room temperature, carries out ultrasonic response, electrostatic field treatment time 30min, and 80 ℃ of temperature, strength of electric field 400V/cm, other conditions are with embodiment mono-, and test-results is in Table 5.
Table 5
Claims (10)
1. from hydrocarbon ils, remove a method for nickel and vanadium, comprising:
(1), between 20～150 ℃, use ultrasonication hydrocarbon ils, the viscosity≤100mm of described hydrocarbon ils under treatment temp
2/ s, with the time of ultrasonication hydrocarbon ils be 5～60min, ultrasonic amplitude is 25～112 μ m, frequency is 15kHz～130kHz;
(2) hydrocarbon ils after ultrasonication is mixed with emulsion splitter and water, under electric field action, after breaking emulsion and dewatering, isolate oil phase;
(3) in step (1) or step (2), add metal remover;
Wherein, described hydrocarbon ils is the mixture of component A or component A and B component; Component A is selected from one or more in crude oil, long residuum or vacuum residuum, and B component is selected from the petroleum fractions of boiling point between 100～350 ℃ or one or more in petroleum products; The quality of hydrocarbon ils of take is benchmark, and the content of vanadium in hydrocarbon ils is 5～1000ppm, and the nickel content in hydrocarbon ils is 2～500ppm.
2. in accordance with the method for claim 1, it is characterized in that, the quality of hydrocarbon ils of take is benchmark, and the content of vanadium in hydrocarbon ils is 20～500ppm, and the nickel content in hydrocarbon ils is 5～250ppm.
3. in accordance with the method for claim 1, it is characterized in that, described petroleum fractions is kerosene or solar oil, and described petroleum products is solvent oil.
4. in accordance with the method for claim 1, it is characterized in that, described metal remover is selected from one or more in inorganic phosphate and salt, organic phospho acid and salt thereof, sulfonic acid, halogenated carboxylic acid, cyanic acid and salt thereof, thiocyanic acid and salt thereof, isocyanic acid and salt thereof and isocyanic ester.
5. in accordance with the method for claim 4, it is characterized in that, described metal remover is selected from one or more in following compounds: phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, tetra-sodium, Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid, CH
3pO
3h
2, phosphoramidic acid, methylsulfonic acid, two methylsulfonic acids, Phenylsulfonic acid, naphthene sulfonic acid, methyl-sulfinic acid, trifluoroacetic acid, trichoroacetic acid(TCA) and tolylene diisocyanate.
6. in accordance with the method for claim 1, it is characterized in that, the quality of hydrocarbon ils of take is benchmark, and the consumption of metal remover is 100～10000 μ g/g.
7. in accordance with the method for claim 1, it is characterized in that, in step (1), by the mode of ultrasonication hydrocarbon ils, adopt the mode of intermittent action.
8. in accordance with the method for claim 1, it is characterized in that, in step (1), ultrasonic frequency is 20kHz～40kHz.
9. in accordance with the method for claim 1, it is characterized in that, in step (1), ultrasonic amplitude is 75～100 μ m.
10. in accordance with the method for claim 1, it is characterized in that, the operational condition of step (2) is: the quality of hydrocarbon ils of take is benchmark, and the consumption of emulsion splitter is 10～200 μ g/g; The quality of hydrocarbon ils of take is benchmark, and the consumption of water is 3%～20%; The temperature of breaking emulsion and dewatering is 60～145 ℃; Electric-force gradient is 200～2000V/cm.
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|---|---|---|---|
| CN201010177792.1A CN102250640B (en) | 2010-05-20 | 2010-05-20 | Method for removing nickel and vanadium from hydrocarbon oil |
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|---|---|---|---|
| CN201010177792.1A CN102250640B (en) | 2010-05-20 | 2010-05-20 | Method for removing nickel and vanadium from hydrocarbon oil |
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| CN102250640B true CN102250640B (en) | 2014-03-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374385B (en) * | 2012-04-17 | 2015-07-01 | 中国石油化工股份有限公司 | Composition with effect of removing heavy metals in hydrocarbon oil as well as preparation method and application of composition |
| CN103374414B (en) * | 2012-04-17 | 2015-07-01 | 中国石油化工股份有限公司 | Method for removing nickel and vanadium from hydrocarbon oil |
| CN103937529B (en) * | 2013-01-22 | 2015-12-23 | 中石化洛阳工程有限公司 | A kind of crude oil metal remover |
| CN106032471B (en) * | 2015-03-17 | 2018-03-20 | 中国石油化工股份有限公司 | The charging method of metal remover composition, metal remover emulsion and metal remover |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2539559Y (en) * | 2002-03-28 | 2003-03-12 | 中国石化集团齐鲁石油化工公司 | Crude oil ultrasonic wave-electric field combined desalination device |
| CN1693424A (en) * | 2005-06-01 | 2005-11-09 | 华东理工大学 | Process for demetalizating of hydrocarbon oil |
| CN101381620A (en) * | 2008-10-24 | 2009-03-11 | 辽宁石油化工大学 | Demetalization method of oil products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2539559Y (en) * | 2002-03-28 | 2003-03-12 | 中国石化集团齐鲁石油化工公司 | Crude oil ultrasonic wave-electric field combined desalination device |
| CN1693424A (en) * | 2005-06-01 | 2005-11-09 | 华东理工大学 | Process for demetalizating of hydrocarbon oil |
| CN101381620A (en) * | 2008-10-24 | 2009-03-11 | 辽宁石油化工大学 | Demetalization method of oil products |
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