CN101220293A - Method for ion liquid abstraction-catalytic oxidation desulfurization - Google Patents
Method for ion liquid abstraction-catalytic oxidation desulfurization Download PDFInfo
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Abstract
The invention relates to a method which uses ionic liquids extraction coupling tungsten, molybdenum and other polyoxometallate to catalyst oxidation so as to reduce the content of sulfur in the oil. The invention dissolves the catalyst into the ionic liquid and the volume ratio of the ionic liquid and the oil is 1:3 to 1:5, and the quantity range of the catalyst and the sulfur compounds is 1:100 to 4:100. The concentration of the aqueous hydrogen peroxide is 5 percent to 40 percent, and the content range with the sulfur compounds in the oil is 1:2 to 1:10. When the temperature is between 30 and 70 DEG C and the reaction time is 0.5 to 3 hours, coupling catalyst oxidation is extracted to reduce the content of sulfur in the oil to be less than 10 ppm. Compared with the traditional method, the method has the advantages that the sulfur has high removal efficient, and the reaction system is very simple, and the reaction condition is very soft and no pressure equipment is needed; the separation is very convenient and the ionic liquid can be recycled.
Description
Technical field
The present invention relates to a kind of method of ion liquid abstraction coupling polyoxometallate catalyzing hydrogen peroxide oxidation reduction sulfur in gasoline content.
Background technology
Sulfocompound in the gasoline can produce a large amount of sulfurous gas in combustion processes, sulfurous gas is the major cause that acid rain forms, and can cause large-scale environmental pollution thus, and the eubiosis of the earth in serious threat.More and more strictly for sulfur content in gasoline, the sulfur content of U.S.'s diesel oil in 2006 and gasoline requires to be lower than 15ppm and 30ppm to the requirement of sulfur content in gasoline in countries in the world; It is below the 30ppm that Europe requires sulfur content in gasoline at present, then requires below the 50ppm for the sulfur content in the diesel oil.At present, the standard of China's sulfur in gasoline is to be lower than 800ppm, and is very big from the gap of developed country.China promises to undertake that city such as Beijing and Shanghai fuel oil quality index reaches Europe VI standard (50ppm) during the course of the Olympic Games, and its task is quite arduous.At present, the hydrodesulfurization of industrial extensive employing (HDS) is though inorganic sulfur and the part organosulfur in can effective elimination gasoline is very low to the desulfuration efficiency that has substituent thiophene, thionaphthene, dibenzothiophene and other thiophene derivant.For this reason, each state has all strengthened the research to other degree of depth process for sulfur removal, and as oxidation sweetening method, liquid-phase extraction method, direct absorption method, biological desulphurization method etc., wherein, the oxidation sweetening method is acknowledged as a very promising desulfurization technology.Carbon-sulfur bond is approximate nonpolarity in the thiophene-type sulfide, and with corresponding organic carbon hydrogen compound similar performance, both solvabilities in water or polar solvent are much at one.But the sulfoxide that generates after the oxidation and the solubility of sulfone class organic oxygen-containing compound in water or polar solvent are greater than its corresponding organic carbon hydrogen compound.Therefore, oxygen atom is linked on the sulphur atom of thiophenes by oxidation, just can be increased its polarity and make it easier of polar solvent extract, thereby reach purpose with separation of hydrocarbons.
To be that exploitation is a kind of have high reactivity and catalytic oxidation system optionally to removing sulfide in petrol to the key of oxidation sweetening method.
The organic liquid material that ionic liquid namely is made of ion under room temperature or near room temperature temperature.Ionic liquid is compared with organic solvent commonly used unique character, does not almost have vapour pressure such as (1), is using, can not evaporate in the storage lost, can recycle, and free from environmental pollution; High heat endurance and chemical stability are arranged, and are liquid in broad temperature range, are conducive to dynamics Controlling; (2) have good dissolubility, they show good solvability to inorganic and organic compound.By can regulating its solvability to inorganics, water, organism and polymkeric substance to yin, yang ionic appropriate design, and its acidity can transfer to super acid; (3) there are not combustibility, no point of ignition; (4) ionic conductivity height, electrochemical window is big, and it is many to reach 3～5V.The eighties is early stage, and research institutions such as K.Seddon, Britain BP company France IFP begin systematically to explore the possibility of ion as solvent and catalyzer.Now, ionic liquid is very active with the research in fields such as catalyzing and synthesizing for extract and separate.
Calendar year 2001, ionic liquid be applied to abstraction desulfurization research (Chem.Commun., 2001,2494-2495), mainly reported (C in the document
4MimCl)/AlCl
3Ionic liquid mixes with the fuel oil phase, and then is separated with oil fuel, can remove the organosulfurs such as dialkyl group dibenzothiophene in the oil fuel, and the decreasing ratio of sulphur is 50%.Also investigated [C simultaneously
4Mim] PF
6, [C
4Mim] BF
4, [C
4Mim] [CF
3SO
3] and [C
8Mim] [OcSO
4] plasma liquid is to the removal effect of oil fuel, the result shows that independent abstraction desulfurization rate is relatively low, is about 30%.Chinese patent 200410097570.3 has been reported 1-decyl-3 Methylimidazole fluoroborate, the method for 1-decyl-3 Methylimidazole fluorophosphate plasma liquid extraction desulfurization, and the rate of taking off is 50-60%.Bao Dao ionic liquid also had [C afterwards
4Mim] Cl, [C
4Mim] Br, [C
4Mim] Cl/CuCl, [C
4Mim] Cl/ZnCl
2, [C
4Mim] Cl/SnCl
2, tertiary amine/AlCl
3, trimethylamine hydrochloride/AlCl, [C
2Mim] [EtSO
4], [C
4Mim] [OcSO
4], [C
6Mim] [Tf
4N] and the phosphoric acid ester ionic liquid etc., these ionic liquids have mainly been investigated the effect of abstraction desulfurization aspect, must all have the lower problem of decreasing ratio of sulphur.
2003, (Green.Chem., 2003 such as Lo, 639-642) research method is improved, studied ionic liquid and aqueous hydrogen peroxide solution/acetate mixed system and be used for the desulfurization of fuel oil, this system is ion liquid abstraction desulfurization and chemical oxidation combination, and the ionic liquid of use mainly is [C
4Mim] PF
6, [C
8Mim] PF
6, [C
4Mim] BF
4[C
8Mim] BF
4Lu etc. (Energy and Fuels, 2007,21,383-384) to have studied and added aqueous hydrogen peroxide solution in the acidic ion liquid, the desulfurization degree of this ion liquid abstraction and chemical oxidation coupled sulfur method can reach 90%.
Summary of the invention
The object of the present invention is to provide a kind of extraction catalytic oxidation desulfurization system that in ionic liquid, forms with tungsten, molybdenum multi-metal oxygen phosphate catalyst and aqueous hydrogen peroxide solution, reduce the method for sulfur content in gasoline by the extraction catalytic oxidation, such catalyst can both be dissolved in the ionic liquid before and after reaction, and ionic liquid and oil phase do not dissolve each other.This so that reaction finish after the separation of oil phase become very simple, remaining ionic liquid and catalyst can recycle through simple process.
Used solvent is that ionic liquid is avoided with an organic solvent among the present invention, and used ionic liquid is that negatively charged ion is selected from Cl in the ionic liquid
-, Br
-, BF
4 -, PF
6 -, HSO
4 -, CF
3CO
2 -In a kind of; Positively charged ion is selected from [C
mMim] in a kind of, wherein m is 4,6,8.
The catalyst that the present invention uses has: (I) Y
2MO
4.nH
2O, wherein Y represents H, Na, K or NH
4Wherein M represents Mo or W.Preferred catalyst is sodium tungstate, sodium molybdate, wolframic acid.(II) contain the polyoxometallate of phase transition group, its molecular formula is:
[R
1R
2R
3R
4N]
4W
10O
32；
Or [R
1R
2R
3R
4N]
2W
2O
3(O
2)
4
Or [R
1R
2R
3R
4N]
3{ PO
4[WO (O
2)
2]
4}
Or [R
1R
2R
3R
4N]
3XM
mM
1 12-mO
40(X=P, As; M, M
1=Mo, W);
Or [R
1R
2R
3R
4N]
6X
2M
nM
1 18-nO
62(X=P, As; M, M
1=Mo, W);
Or [π-C
5H
5NR
1]
4W
10O
32
Or [π-C
5H
5NR
1]
2W
2O
3(O
2)
4
Or [π-C
5H
5NR
1]
3{ PO
4[WO (O
2)
2]
4}
Or [π-C
5H
5NR
1]
3XM
mM
1 12-mO
40(X=P, As; M, M
1=Mo, W);
Or [π-C
5H
5NR
1]
6X
2M
nM
1 18-nO
62(X=P, As; M, M
1=Mo, W);
Or (L)
4W
10O
32
Or WO (O
2)
2L
Or (L)
2W
2O
3(O
2)
Or (L)
3{ PO
4[WO (O
2)
2]
4}
Or (L)
pXM
mM
1 12-mO
40(X=P or As; M, M
1=Mo or W); P=(3 or 4)
Or (L)
6X
2M
nM
1 18-nO
62(X=P or As; M, M
1=Mo or W);
In the formula:
R
1, R
2, R
3, R
4Represent respectively carbon number and be in 1～18 the alkyl any, can equate, also can not wait.Preferred alkyl is a tetramethyl-, tetraethyl-, tetrapropyl, the tetrabutyl, benzyl triethyl ammonium.
L represents oxine or phenanthroline.
m＝0～12；
n＝0～18
These catalyzer can be good at being dissolved in the ionic liquid in heated and stirred a little, all are dissolved in the ionic liquid before and after the reaction.
Used oxygenant is an aqueous hydrogen peroxide solution in the process of the present invention, and the concentration of aqueous hydrogen peroxide solution is 5%-40%, with the scope of sulfur in gasoline compound mol ratio be 1: 2-1: 10.
The scope of the mole ratio of catalyst system therefor and sulfur in gasoline compound is 1 in the process of the present invention: 100-4: 100.
The volume ratio of used ionic liquid and gasoline is 1 in the process of the present invention: 5-1: 3.
Oxidation reaction condition gentleness of the present invention, temperature of reaction are between 30 to 70 ℃, and temperature of reaction is between 40 to 70 ℃ preferably.
The present invention and traditional reaction process relatively have the following advantages:
1. hydrogen peroxide is the stronger Green Oxidant of oxidisability, and therefore, this reaction condition gentleness does not need pressurized equipment, and is without the need for the machine solvent, harmless to human and environment.
2. the catalyst activity and selectivity that screens is good, the removal efficiency height of sulphur, and sulfur content can drop to below 10 ppm.
3. ionic liquid and oil phase do not dissolve each other, and ionic liquid separated with fuel oil simply after reaction finished, and ionic liquid can recycle.
Embodiment
Give further instruction below by example to the present invention.
The preparation of oil product is incited somebody to action: dibenzothiophene (DBT) is dissolved in the octane, and being made into S content is the 1000ppm simulated oil.
Example 1 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 1mL
4Mim] [BF
4] the inner catalyst that adds 0.00052mmol: H
3PW
12O
40With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 1h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 75.6% by the removal efficiency that calculates sulphur.
Example 2 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [PF
6] the inner catalyst that adds 0.00052mmol: H
3PMo
12O
40With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 1h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 62.6% by the removal efficiency that calculates sulphur.
Example 3 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [PF
6] the inner catalyst that adds 0.00052mmol: H
3SiMo
12O
40With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 60 ℃ of lower magnetic forces stir 1h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 68.6% by the removal efficiency that calculates sulphur.
Example 4 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [CF
3CO
2] the inner catalyst that adds 0.00052mmol: (NH
4)
3PMo
12O
40With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 40 ℃ of lower magnetic forces stir 1h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 52.6% by the removal efficiency that calculates sulphur.
Example 5 is in having two neck reaction bulbs of magnetic agitation, to ionic liquid [the bmim] [BF of 2mL
4] the inner catalyst that adds 0.00624mmol: Na
2WO
42H
2O and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 98.8% by the removal efficiency that calculates sulphur.
Example 6 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] HSO
4In add the catalyst of 0.00624mmol: H
2WO
4With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 97.8% by the removal efficiency that calculates sulphur.
Example 7 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] BF
4In add the catalyst of 0.00624mmol: H
2MoO
4With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 96.9% by the removal efficiency that calculates sulphur.
Example 8 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00078mmol: [(C
4H
9)
4]
4W
10O
32With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 98.6% by the removal efficiency that calculates sulphur.
Example 9 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [PF
6] the inner catalyst that adds 0.00312mmol: [(C
7H
7C
12H
25N (CH
3)
2]
4W
2O
3(O
2)
4With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 92.5% by the removal efficiency that calculates sulphur.
Example 10 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [BF
4] the inner catalyst that adds 0.00052mmol: [(C
4H
9)
4]
4PWMo
11O
40With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 95.5% by the removal efficiency that calculates sulphur.
Example 11 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [PF
6] the inner catalyst that adds 0.00078mmol: [π-C
5H
5NC
16H
33]
3W
10O
32With 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 96.2% by the removal efficiency that calculates sulphur.
Example 12 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [BF
4] the inner catalyst that adds 0.00156mmol: [(C
4H
9)
4]
4{ PO
4[WO (O
2)
2]
4And 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 97.6% by the removal efficiency that calculates sulphur.
Example 13 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 5h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 99.5% by the removal efficiency that calculates sulphur.
Example 14 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 1h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 50.6% by the removal efficiency that calculates sulphur.
Example 15 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 0.312mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 95.6% by the removal efficiency that calculates sulphur.
Example 16 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 0.624mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 97.6% by the removal efficiency that calculates sulphur.
Example 17 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide molybdic acid 1,10-ferrosin (MoO (O
2)
2Phen) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 93.0% by the removal efficiency that calculates sulphur.
Example 18 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [PF
6] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 96.7% by the removal efficiency that calculates sulphur.
Example 19 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [PF
6] the inner catalyst that adds 0.00624mmol: peroxide molybdic acid 1,10-ferrosin (MoO (O
2)
2Phen) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 97.8% by the removal efficiency that calculates sulphur.
Example 20-23 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, after collecting mutually, ionic liquid in 110 ℃ of oil baths, evaporates place to go residue oil product and H
2O
2, add again fresh 1.56mmol 30%H
2O
2Carry out the next round desulfurization with the 5mL simulated oil.Repeat 4 times (example 5-8), reaction result is as shown in the table:
| Cycle-index | 1 | 2 | 3 | 4 |
| Desulfurization degree (%) | 98.0 | 97.2 | 97.0 | 96.1 |
Example 24 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [BF
4] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 90.5% by the removal efficiency that calculates sulphur.
Example 25 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
8Mim] [PF
6] the inner catalyst that adds 0.00624mmol: peroxide wolframic acid 1,10-ferrosin (WO (O
2)
2PhenH
2O) and 1.56mmol 30%H
2O
2With the 5mL simulated oil, this moment ionic liquid in lower floor, oil phase is on the upper strata, catalyst and H
2O
2Be dissolved in the ionic liquid; After 70 ℃ of lower magnetic forces stir 3h, isolate simulated oil, adopt GC-FID (internal standard method) to detect the content of DBT in the oil, be 97.3% by the removal efficiency that calculates sulphur.
Above-mentioned example shows, adopts ion liquid abstraction coupling and catalyzing oxidation sweetening method of the present invention can reach the purpose of organosulfur in the deep removal gasoline.Catalyst can be dissolved in the ionic liquid in course of reaction, is easy to reclaim together and recycle with ionic liquid.The oxidant that the present invention uses is H
2O
2, be water after the reaction, environmentally friendly.This extraction catalytic oxidation desulfurization system avoids using the poisonous halogenated hydrocarbons of tradition to be solvent, and course of reaction is simple to operation, for the organic sulfur in deep removal gasoline and the diesel oil provides a new process route.
Claims (8)
1. the method for abstraction-catalytic oxidation desulfurization, it is characterized in that: with tungsten, molybdenum multi-metal oxygen hydrochlorate as catalyst dissolution in ionic liquid, the volume ratio of ionic liquid and gasoline is 1: 3-1: 5, catalyzer is 1 with the scope of the amount of substance ratio of sulfur in gasoline compound: 100-4: 100, the concentration of aqueous hydrogen peroxide solution is 5%-40%, with the scope of sulfur in gasoline compound amount of substance be 1: 2-1: 10, at 30-70 ℃, reaction times 0.5-3 hour; The ionic liquid negatively charged ion is selected from Cl
-, Br
-, BF
4 -, PF
6 -, HSO
4 -, CF
3CO
2 -In a kind of; The ionic liquid positively charged ion is selected from [C
mMim]
+In a kind of, wherein m is 4,6,8.
2. by the method for the described abstraction-catalytic oxidation desulfurization of claim 1, it is characterized in that: ionic liquid is [C
4Mim] BF
4, [C
8Mim] BF
4, [C
4Mim] PF
6, [C
8Mim] PF
6
3. by the method for the described abstraction-catalytic oxidation desulfurization of claim 1, it is characterized in that: catalyst is Y
3XM
mM
1 12-mO
40, wherein Y represents H, Na, K or NH
4X represents P, As or Si; M represents Mo; M
1Represent W; M=0～12.
4. by the method for the described abstraction-catalytic oxidation desulfurization of claim 3, it is characterized in that: catalyzer is a phospho-wolframic acid, phospho-molybdic acid.
5. by the method for the described abstraction-catalytic oxidation desulfurization of claim 1, it is characterized in that: catalyst is Y
2MO
4N H
2O, wherein Y represents H, Na, K or NH
4Wherein M represents Mo or W.
6. by the method for the described abstraction-catalytic oxidation desulfurization of claim 5, it is characterized in that: catalyzer is a sodium wolframate, Sodium orthomolybdate, wolframic acid.
7. by the method for the described abstraction-catalytic oxidation desulfurization of claim 1, it is characterized in that: catalyzer is the polyoxometallate that contains the phase transition group, and its molecular formula is:
[R
1R
2R
3R
4N]
4W
10O
32；
Or [R
1R
2R
3R
4N]
2W
2O
3(O
2)
4
Or [R
1R
2R
3R
4N]
3{ PO
4[WO (O
2)
2]
4}
Or [R
1R
2R
3R
4N]
3XM
mM
1 12-mO
40(X=P or As; M=Mo; M
1=W);
Or [R
1R
2R
3R
4N]
6X
2M
nM
1 18-nO
62(X=P or As; M=Mo; M
1=W);
Or [π-C
5H
5NR
1]
4W
10O
32
Or [π-C
5H
5NR
1]
2W
2O
3(O
2)
4
Or [π-C
5H
5NR
1]
3{ PO
4[WO (O
2)
2]
4}
Or [π-C
5H
5NR
1]
3XM
mM
1 12-mO
40(X=P or As; M=Mo; M
1=W);
Or [π-C
5H
5NR
1]
6X
2M
nM
1 18-nO
62(X=P or As; M=Mo; M
1=W);
Or (L)
4W
10O
32
Or WO (O
2)
2L
Or (L)
2W
2O
3(O
2)
Or (L)
3{ PO
4[WO (O
2)
2]
4}
Or (L)
pXM
mM
1 12-mO
40(X=P or As; M=Mo; M
1=W);
Or (L)
pX
2M
nM
1 18-nO
62(X=P or As; M=Mo; M
1=W);
In the formula: R
1, R
2, R
3, R
4Representing carbonatoms respectively is 1～18 alkyl, equates, or does not wait; L represents oxine or phenanthroline;
m＝0～12；
n＝0～18；
p＝3，4，6。
8. by the method for the described abstraction-catalytic oxidation desulfurization of claim 1, it is characterized in that: described alkyl is tetramethyl-, tetraethyl-, tetrapropyl, the tetrabutyl or benzyl triethyl ammonium.
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