CN102732287B - Super-deep fuel desulphurization method - Google Patents

Super-deep fuel desulphurization method Download PDF

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CN102732287B
CN102732287B CN201110090115.0A CN201110090115A CN102732287B CN 102732287 B CN102732287 B CN 102732287B CN 201110090115 A CN201110090115 A CN 201110090115A CN 102732287 B CN102732287 B CN 102732287B
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thiophene
hydrogen peroxide
ionic liquid
oil
sulfocompound
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CN102732287A (en
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李�灿
张博宇
蒋宗轩
刘龑
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a super-deep fuel oxidation desulphurization method, and especially relates to a method for super-deep oxidation removal of thiophene sulfocompounds from a fuel. A catalytic system, provided in the invention and used for the super-deep oxidation removal of the thiophene sulfocompounds, comprises a Bronsted acidic ionic liquid and a catalytic amount of a late transition metal salt (W, Mo), and the method adopts 30% hydrogen peroxide as an oxidant. Sulfur atoms in the thiophene sulfocompounds can be converted into sulfate radicals with hydrogen peroxide as the oxidant in the presence of the catalytic system, and the sulfate radicals can be removed through simple washing. The desulphurization method has the characteristics of simple process, mild reaction condition, low operation cost and the like. After reaction ending and fuel separation, the catalytic system can be repeatedly used after simple extraction, and the removal efficiency does not decrease. The removal rate of the thiophene compounds from the fuel through the method of the invention can reach 99.5%.

Description

A kind of ultra-deep desulfurization of fuel method
Technical field
The present invention relates to a kind of super deep oxidation desulfurization method of fuel oil.
Background technology
Due to stricter environmental legislation, ultra-deep desulfurization of fuel (< 10ppm sulphur) has become the worldwide research topic that very urgent urgent need solves.Although traditional hydrogenating desulfurization can remove the sulfur-containing molecules in gasoline very effectively, but it is also saturated by hydrogenation in desulfurization, to be present in a large amount of alkene in gasoline, and this certainly will produce following problems: hydrogen consumption is high, process cost is high, the serious problem that reduces etc. of gasoline octane rating.
In fuel cell system, no matter be gasoline reforming hydrogen manufacturing part or fuel battery engines part, all must under without sulphur condition, carry out.Because the noble metal of using in these parts (as platinum etc.) is easy to irreversible sulfur poisoning.Thereby exploitation ultralow density or sweet gasoline are also very urgent research topics.
Based on above reason, exploitation super low sulfur (< 10ppm sulphur) or sweet gasoline (< 0.1ppm sulphur) become domestic and international field with keen competition at present.The ultra-deep desulfurization method of developing in the world at present has: adsorption desulfurize, oxidation sweetening, abstraction desulfurization and biological desulphurization etc.The sulfocompound that utilizes ion liquid abstraction to remove in petroleum fractions has fragmentary report, as research shows that glyoxaline ion liquid has good extraction (as: patent CN200610066595, CN200410037677 and CN03137916) to main sulfurous organic compound in the fuel oils such as thiophene, thionaphthene, dibenzothiophene.But the shortcomings such as desulfuration efficiency is low, ionic liquid consumption is large that these class methods exist.
Patent CN101220293 has developed a kind of method of abstraction-catalytic oxidation desulfurization.The method can be utilized the fine oxidation removal dibenzothiophene of oxidation susceptibility and the derivative thereof of the extraction of ionic liquid and tungsten, molybdenum salt.But for the important sulfocompound thiophene and derivatives in gasoline, rarely have the example of report about its oxidation sweetening in document, its reason is thiophene and derivatives, and the electron density on its sulphur atom is less, is difficult to oxidized.
Summary of the invention
The object of the present invention is to provide a kind of efficient, catalytic oxidation system removing for fuel oil sulfocompound of being easy to recycle.
For achieving the above object, the technical solution used in the present invention is:
Select
Figure DEST_PATH_GDA0000076691430000011
acidic ion liquid is as extraction agent, and reaction solvent and co-catalyst, pass through
Figure DEST_PATH_GDA0000076691430000012
interaction between the acid homoaromaticity sulfocompound weakly alkaline of acidic ion liquid weakens the conjugated nature of aromaticity sulfocompound, increase the electron density of sulphur atom on sulfocompound, make it can be effectively by hydrogen peroxide oxidation under the existence of tungsten-containing catalyst.
Present method is used
Figure BDA0000054676780000024
acidic ion liquid is as follows:
HnmpX；HmimX；HcpX；HpyX；
Figure BDA0000054676780000025
Hnmp Hmim Hcp Hpy
The N-methyl pyrrole that Hnmp=is protonated alkane ketone; The N-Methylimidazole that Hmim=is protonated; The hexanolactam that Hcp=is protonated; The butyrolactam that Hpy=is protonated;
X＝BF 4，PF 6，NO 3，HSO 4，H 2PO 4，C 5H 5NCO 2，CH 3SO 3，CF 3SO 3，CF 3CO 2，CH 3CO 2
Concrete steps are:
A) under normal temperature and pressure, by fuel oil, acidic ion liquid, catalyzer, hydrogen peroxide fully mix, reaction 10-300 minute, sulfocompound in fuel oil is converted into sulfone or sulfate radical, and the sulfone of generation or sulfate radical are extracted among ionic liquid, and upper strata obtains sulphur content < 10ppm super low sulfur fuel oil;
Described
Figure BDA0000054676780000027
the mass ratio of acidic ion liquid and fuel oil is 1: 1～1: 100;
In the amount of described hydrogen peroxide and fuel oil, the mol ratio of sulfocompound is 5: 1～50: 1;
In described catalyzer and fuel oil, the mol ratio of sulfocompound is 1: 5～1: 100;
B) Separation and Recovery ionic liquid phase, it can carry out recycling next time.
Described fuel oil refers to the gasoline, diesel oil or the kerosene that contain thiophene and derivatives, and to be wherein scaled element sulphur content be 50ppm～2000ppm to sulfocompound.
The present invention prepares the method for super low sulfur fuel oil with above-mentioned catalytic oxidation system, key step is: by 0.5～50g containing than sulfocompound 1～20mol% catalyzer
Figure BDA0000054676780000028
acidic ion liquid and mass concentration be 1%～30% hydrogen peroxide by oxygen sulphur ratio be 5～50 mix after, add 700ng/ul model gasoline 50g, under 25～90 DEG C, 0.1～1MPa condition, stirring reaction 10～300min, stopped reaction, Separation and Recovery oil reservoir and ionic liquid phase.
Described catalyzer is
(NH 4) 10h 2(W 2o 7) 6h 2o, H 2wO 4, NaWO 42H 2o, WO 3, H 3pW 12o 40xH 2o, (NH 4) Mo 7o 244H 2o, H 2moO 4, Na 2moO 42H 2o, MoO 3, V 2o 5in one or two or more kinds.
Described sulfur compound is thiophene, 2-thiotolene, 3 methyl thiophene, one or more in 2,5-thioxene.
Compared with known technology, the present invention has the following advantages:
1, present method is exceedingly fast to the oxidation removal speed of sulfocompound in model gasoline, and efficiency is high.
2, using hydrogen peroxide is oxygenant, non-environmental-pollution.Can be directly sulfuric acid by the oxidized sulfur atom in the middle of thiophene and derivatives, sulfuric acid enters ionic liquid and directly obtains mutually the mould oil of ultra-low sulfur.
3, ionic liquid can be recycled through simple processing.
4, application present method oil product free of losses in model gasoline sulfocompound subtractive process.
5, the present invention with
Figure BDA0000054676780000031
the dual-active mechanismic design of acidic ion liquid activation thiophene sulfocompounds and late transition metal salt catalyst oxidation.In above-mentioned catalyst system exists, the sulphur atom in thiophene sulfocompounds is at hydrogen peroxide as being converted to sulfate radical under oxygenant, and it can simply be washed and remove.This sulfur method has the features such as process is simple, reaction conditions is gentle, process cost is low.After reaction finishes, after fuel oil separates, catalyst system is reusable after simple extraction, and removal efficiency does not all reduce.Method of the present invention can reach 99.5% to the decreasing ratio of thiophenes in fuel oil.
Brief description of the drawings
Fig. 1 contains catalyzer acidic ion liquid [Hnmp] BF 4recycle design sketch
The barium sulfate precipitate XRD spectra of Fig. 2 thiophene oxidation products sulfate radical
The GC-MS of Fig. 3 thiophene oxidation products analyzes
The strategy of the dual-active oxidation of thiophene that Fig. 4 is new
Embodiment
In order to further illustrate the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add (the NH of 1mol% (with respect to the molar ratio of sulfocompound, as thiophene) 4) 10h 2(W 2o 7) 6h 2o, then the hydrogen peroxide that the massfraction that to add with sulfocompound mol ratio be 10 is 30%, finally adds the thiophene of 20ml 700ng/ul to be dissolved in the fuel oil of octane, and now ionic liquid is in lower floor, oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 99.6% by the decreasing ratio of external standard method sulphur.
Question response finishes, separate ionic liquid phase, steam after 1 hour at 70 DEG C of backspins, the thiophene that rejoins 20ml700ng/ul is dissolved in the fuel oil of octane, the hydrogen peroxide that is 30% with the sulfocompound mol ratio massfraction that is 10 stirs after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, by the decreasing ratio of external standard method sulphur.The situation of reusing of the ionic liquid that contains catalyzer is shown in Fig. 1.
Get the ionic liquid 2g after reaction repeated, add wherein saturated nitrate of baryta solution, occur immediately white precipitate, collect white precipitate and prove barium sulfate generation (Fig. 2) through XRD.Get 1g ionic liquid, use extracted with diethyl ether three times, after concentrating, detect and have phenylformic acid through GC-MS, phenyl aldehyde generates (Fig. 3).
Embodiment 2
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the H of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2wO 4, and the hydrogen peroxide of massfraction 30% of 10 molar equivalents and the thiophene of the 700ng/ul of 20ml be dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 98% by the decreasing ratio of external standard method sulphur.
Embodiment 3
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the Na of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2wO 42H 2o, and the thiophene of the 700ng/ul of the massfraction of the 10 molar equivalents hydrogen peroxide that is 30% and 20ml is dissolved in the mould oil of octane, now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 97.8% by the decreasing ratio of external standard method sulphur.
Embodiment 4
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add, the WO of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 3, and the thiophene of the 700ng/ul of the massfraction of the 10 molar equivalents hydrogen peroxide that is 30% and 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 21% by the decreasing ratio of external standard method sulphur.
Embodiment 5
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the H of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 3pW 12o 40xH 2o, and the thiophene of the 700ng/ul of the massfraction of the 10 molar equivalents hydrogen peroxide that is 30% and 20ml is dissolved in the mould oil of octane, now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 19.5% by the decreasing ratio of external standard method sulphur.
Embodiment 6
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add (the NH of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 4) Mo 7o 244H 2o, and the thiophene of the 700ng/ul of the massfraction of the 10 molar equivalents hydrogen peroxide that is 30% and 20ml is dissolved in the mould oil of octane, now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 36.4% by the decreasing ratio of external standard method sulphur.
Embodiment 7
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the H of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2moO 4, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 32.6% by the decreasing ratio of external standard method sulphur.
Embodiment 8
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the Na of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2moO 42H 2o, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 25.4% by the decreasing ratio of external standard method sulphur.
Embodiment 9
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the MoO of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 3, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 16.7% by the decreasing ratio of external standard method sulphur.
Embodiment 10
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hnmp] BF 4in add the V of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2o 5, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 22.6% by the decreasing ratio of external standard method sulphur.
Embodiment 11
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hmim] BF 4in add the V of 2mol% (with respect to the molar ratio of sulfocompound, as thiophene) 2o 5, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 22.6% by the decreasing ratio of external standard method sulphur.
Embodiment 12
Being furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, to 1ml ionic liquid [Hmim] BF 4, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, and now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stirring after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, is 18.5% by the decreasing ratio of external standard method sulphur.
Embodiment 13
Be furnished with in the middle of the round-bottomed flask with magnetic agitation of prolong, adding (the NH of 2mo1% (with respect to the molar ratio of sulfocompound, as thiophene) 4) 10h 2(W 2o 7) 6h 2o, and the thiophene of 30% hydrogen peroxide of 10 molar equivalents and the 700ng/ul of 20ml is dissolved in the mould oil of octane, now ionic liquid is in lower floor, and oil phase is on upper strata, and catalyzer and hydrogen peroxide are dissolved in ionic liquid; Stir after 5h at 60 DEG C of lower magnetic forces, isolate mould oil, adopt the content of the central thiophene of GC-FPD detection model oil, by the decreasing ratio of external standard method sulphur, sulfocompound does not remove substantially.All embodiment above, all catalyzer can be reused.
The oxidation removal of the different catalyst system of table 1 to thiophene
In sum, the present invention has developed one
Figure BDA0000054676780000062
acidic ion liquid and tungstate catalysts are total to the method for catalysis for oxidation sweetening.Under gentle reaction conditions (20～80 DEG C, 1atm), taking hydrogen peroxide as oxygenant, the method can be removed to the sulfocompound in the middle of fuel oil below 10ppm.Compare oxidation sweetening system in the past, present method can successfully remove high conjugation, be difficult to the sulfocompound thiophene and derivatives of oxidation.Reusable by simple separatory, and catalytic activity does not have heavy losses.

Claims (5)

1. a method for ultra-deep desulfurization of fuel, is characterized in that, concrete steps are:
A) under normal temperature and pressure, by fuel oil,
Figure FDA0000054676770000011
acidic ion liquid, catalyzer, hydrogen peroxide fully mix, reaction 10-300 minute, and upper strata obtains sulphur content < 10ppm super low sulfur fuel oil;
Described
Figure FDA0000054676770000012
the mass ratio of acidic ion liquid and fuel oil is 1: 1～1: 100;
In the amount of described hydrogen peroxide and fuel oil, the mol ratio of sulfocompound is 5: 1～50: 1;
In described catalyzer and fuel oil, the mol ratio of sulfocompound is 1: 5～1: 100;
B) Separation and Recovery ionic liquid phase, it can carry out recycling next time.
2. in accordance with the method for claim 1, it is characterized in that: described fuel oil refers to the gasoline, diesel oil or the kerosene that contain thiophene and derivatives, to be wherein scaled element sulphur content be 50ppm～2000ppm to sulfocompound.
3. it is characterized in that in accordance with the method for claim 1: described
Figure FDA0000054676770000013
acidic ion liquid is one or two or more kinds in following substances:
HnmpX；HmimX；HcpX；HpyX；
Figure FDA0000054676770000014
Hnmp Hmim Hcp Hpy
The N-methyl pyrrole that Hnmp=is protonated alkane ketone; The N-Methylimidazole that Hmim=is protonated; The hexanolactam that Hcp=is protonated; The butyrolactam that Hpy=is protonated
X=BF 4 -, PF 6 -, NO 3 -, HSO 4 -, H 2pO 4 -, C 5h 5nCO 2 -, CH 3sO 3 -, CF 3sO 3 -, CF 3cO 2 -, or CH 3cO 2 -.
4. in accordance with the method for claim 1, it is characterized in that, described catalyzer is (NH 4) 10h 2(W 2o 7) 6h 2o, H 2wO 4, NaWO 42H 2o, WO 3, H 3pW 12o 40xH 2o, (NH 4) Mo 7o 244H 2o, H 2moO 4, Na 2moO 42H 2o, MoO 3, V 2o 5in one or two or more kinds.
5. in accordance with the method for claim 1, it is characterized in that, described sulfur compound is thiophene, 2-thiotolene, 3 methyl thiophene, one or more in 2,5-thioxene.
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CN1690171A (en) * 2004-04-29 2005-11-02 中国石油化工股份有限公司 Supported catalyst, its preparation and use in hydrodesulphurization and olefin-reducing techniques for gasoline
CN101220293A (en) * 2007-09-26 2008-07-16 江苏大学 Method for ion liquid abstraction-catalytic oxidation desulfurization

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690171A (en) * 2004-04-29 2005-11-02 中国石油化工股份有限公司 Supported catalyst, its preparation and use in hydrodesulphurization and olefin-reducing techniques for gasoline
CN101220293A (en) * 2007-09-26 2008-07-16 江苏大学 Method for ion liquid abstraction-catalytic oxidation desulfurization

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