CN103242903A - Fuel desulfurization method - Google Patents
Fuel desulfurization method Download PDFInfo
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- CN103242903A CN103242903A CN2013100480273A CN201310048027A CN103242903A CN 103242903 A CN103242903 A CN 103242903A CN 2013100480273 A CN2013100480273 A CN 2013100480273A CN 201310048027 A CN201310048027 A CN 201310048027A CN 103242903 A CN103242903 A CN 103242903A
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- 239000000446 fuel Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 23
- 230000023556 desulfurization Effects 0.000 title abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 59
- 239000003377 acid catalyst Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- -1 pyrazoles Methylsulfate Chemical class 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 6
- 235000003599 food sweetener Nutrition 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003765 sweetening agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 5
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 3
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical class CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 2
- RILPVBCCHVYIJF-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCN1CN(C)C=C1 RILPVBCCHVYIJF-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229940067741 sodium octyl sulfate Drugs 0.000 claims description 2
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000003009 desulfurizing effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 27
- 239000005864 Sulphur Substances 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 2
- BLZKSRBAQDZAIX-UHFFFAOYSA-N 2-methyl-1-benzothiophene Chemical compound C1=CC=C2SC(C)=CC2=C1 BLZKSRBAQDZAIX-UHFFFAOYSA-N 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- WOKQGMYCUGJNIJ-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CN1C=C[N+](C)=C1 WOKQGMYCUGJNIJ-UHFFFAOYSA-M 0.000 description 1
- KIDIBVPFLKLKAH-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;octyl sulfate Chemical compound CCCCN1C=C[N+](C)=C1.CCCCCCCCOS([O-])(=O)=O KIDIBVPFLKLKAH-UHFFFAOYSA-M 0.000 description 1
- OSCREXKVIJBLHA-UHFFFAOYSA-M 1-ethyl-2,3-dimethylimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCN1C=C[N+](C)=C1C OSCREXKVIJBLHA-UHFFFAOYSA-M 0.000 description 1
- VRFOKYHDLYBVAL-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCN1C=C[N+](C)=C1 VRFOKYHDLYBVAL-UHFFFAOYSA-M 0.000 description 1
- IXLWEDFOKSJYBD-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;methanesulfonate Chemical compound CS([O-])(=O)=O.CC[N+]=1C=CN(C)C=1 IXLWEDFOKSJYBD-UHFFFAOYSA-M 0.000 description 1
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 description 1
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- 150000001449 anionic compounds Chemical class 0.000 description 1
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- CBKJDTFDVVXSJR-UHFFFAOYSA-M methyl sulfate;1,2,4-trimethylpyrazol-2-ium Chemical compound COS([O-])(=O)=O.CC1=CN(C)[N+](C)=C1 CBKJDTFDVVXSJR-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention provides a method for the desulfurization of fuels. During the step (a), an ionic liquid, an oxidizing agent and an acid catalyst are added into the fuel. During the step (b), a desulfurizing agent is added into the oxidized fuel to form a desulfurizing fuel. During the step (c), the ionic liquid is recovered. During the recovery step, a first solution is added into the ionic liquid firstly. Then a second solution is added into the ionic liquid to form a second solution phase and an ion solution phase. After that, the second solution phase is removed. Finally, the first solution, the oxidizing agent and the acid catalyst are removed to obtain the recovered ionic liquid.
Description
Technical field
This area relates to a kind of method with Desulphurization of fuels, and is special, relates to a kind of method of Desulphurization of fuels, and it comprises the step that reclaims ionic liquid.
Background technology
Diesel oil and gasoline are two main transport fuels that use in today.Diesel motor has very big fuel mileage number usually, but diesel oil is usually from crude oil, and crude oil contains the composition of sulphur.Therefore, though diesel oil has high fuel mileage, its benefit is also often offset by the defective of high-sulfur quantity discharged etc.Existing hybrid vehicle, it uses the amount of gasoline to be approximately 50 mile/gallons, approximates the usage quantity of diesel vehicle greatly.Yet diesel vehicle but can produce more quantity discharged usually.Therefore, reducing diesel oil and use quantity discharged, to avoid greenhouse gas emission and to protect environment, is the trend place in the present world.Improve though the technology of diesel motor and discharging is existing, the high sulfur content in the diesel oil still can pollute.
In the time of 2006; according to " Clean Air sct (Clean Air Act) " Environmental Protection Agency (Environmental Protection Agency; EPA) passed through a legislation; sulphur content when limiting 2010 in the road diesel oil fuel be 15 PPMs (parts per million, ppm).By reducing the quantity discharged of SOx, to reduce the negative impact to environment.In general, SOx is the main reason of acid rain, also and the main component of industrial fume.Yet, present ultra-low-sulphur diesel (ultra low sulfur diesel, production ULSD) is subject to inefficient desulfurization technology, and present desulfurization technology there is no too big progress in nearly ten years.
On present commercial applications, with the technology of removing sulphur compound in the fuel adopt mostly hydrodesulfurization (hydrodesulfurization, HDS).Solution in this hydrodesulfurization process need react in 300 to 400 ℃ environment, and needs the participation of hydrogen (hydrogen gas).Yet the environment of High Temperature High Pressure can increase cost, and the danger of blast is arranged in the course of processing.In addition, the mistake of escaping easily of the gas in the system and waste heat also can cause environmental pollution.On the other hand, compared to producing low-sulfur diesel-oil (500ppm), prior art also additionally needs 25% to 45% hydrogen consumption for ultra-low-sulphur diesel (15ppm), shows that such productive technical efficiency is not high.
Therefore, also need a kind of method of Desulphurization of fuels, it can provide better efficient, and has lower pollution.
Summary of the invention
The present invention is in the method that has provided a kind of Desulphurization of fuels, to meet above-mentioned demand.
One of them embodiment according to the present invention the invention provides a kind of method with Desulphurization of fuels.In step (a), an ionic liquid, an oxygenant and an acid catalyst are added in the fuel with oxygenated fuel.In step (b), the fuel after the oxidation is added a sweetening agent to form desulfurized fuel.In step (c), ionic liquid is reclaimed.In the recycling step, at first add one first solution in ionic liquid, follow-up, add one second solution in ionic liquid to form one second solution and a solion phase.Then remove the second solution phase.At last, first solution, oxygenant and acid catalyst are removed, with the ionic liquid that obtains reclaiming.
The present invention can provide a kind of more high-level efficiency and cost-effective method of desulfurization of fuels, and this method comprises many features, for example uses the on-mechanical mixing tank and does not use ultrasonic wave to mix, use ionic liquid, different oxidant concentration and the acid catalyst etc. of regeneration.
Description of drawings
Fig. 1 has represented the block schematic diagram of a continuous-flow system used in the present invention.
Fig. 2 and Fig. 3 have represented the synoptic diagram of a kind of on-mechanical mixing tank among the present invention.
Fig. 4 has represented the nmr spectrum chart of an original ionic liquid.
Fig. 5 has represented the nmr spectrum of the ionic liquid after the recycling.
Wherein, description of reference numerals is as follows:
300 hollow tubes, 302 protuberances
Embodiment
For the those skilled in the art that make the technology of the present invention field can further understand the present invention, hereinafter enumerate several preferred embodiments of the present invention especially, and conjunction with figs., the effect that describes constitution content of the present invention in detail and realize.
The desulfurized step of improvement proposed by the invention includes three parts.Be to utilize an ionic liquid, an oxygenant and an acid catalyst to come oxygenated fuel in first part.At second section, be to utilize a catalyzer to remove the sulphur of the thiophene in the fuel.In third part, then be to use remaining ionic liquid to be reclaimed.
First part be to use a phase-transfer catalysis (phase transfer catalysis, PTC) reaction, with will be in organic phase (organic phase) the sulphur oxidation of thiophene.Generally speaking, phase-transfer-catalyzed reactions comprised for two stages: (1) in water (aqueous phase), the ion-exchange of catalyzer and salt; (2) rate-determing step (rate-determining step) in organic phase (organic phase).In the present invention, phase displacement catalyzed reaction comprises adds an ionic liquid, an oxygenant and an acid catalyst in fuel.
Fuel of the present invention (fuel) can be the fuel oil of the different sulphur content of any kind, for example from crude oil with the various fuel oils of different densities, different extracting process gained, comprise gasoline or Aviation Fuel etc., or even BAKE C oil (Bunker C oil), it is the thick and heavy black residue of other fuel product in the crude oil being removed the back gained.In one embodiment, fuel can be gasoline (gasoline), kerosene (paraffin) or diesel oil (diesel), for example, diesel oil can be that sulphur content is 8, the Valley Oil of 100ppm (from Golden Eagle Oil Refinery, INC. obtain), or the sulphur content of ocean current fuel (marine logistic fuel) is that the JP-5(of 740ppm is from Long Beach, Navy obtains), but be not limited thereto.Can comprise various sulfocompounds in the diesel oil, thiophene (thiophene for example, T), 2-thiotolene (2-methyl thiophene, 2MT), 2 acetyl thiophene (2-ethyl thiophene, 2ET), thionaphthene (benzothiophene, BT), 2-methylbenzene thiophthene (2-methyl benzothiophene, 2MBT), dibenzothiophene (dibenzothiophene, DBT), 4,6-dimethyl Dibenzothiophene (4,6-dimethyl dibenzothiophene, 4,6-DMDBT), 4,6-dibenzothiophene (4,6-dimethyl dibenzothiophene, 4,6-DMDBT), but not as limit.
Oxygenant is used for mercaptan, disulphide or other organosulfur composition (organic sulfur, OCS) for example various thiophene (T), various thionaphthene (BT), or the oxidized sulfur atom in the various dibenzothiophene (DBT), to form sulfone (sulfone) or sulfoxide (sulfoxide).In one embodiment, oxygenant comprises the compound of hypohalite (hypohalite), chlorite (chlorite), permanganate salt ammonium (permanganate salts), cerous nitrate (ammonium cerium) (IV), hexavalent chromium compound (hexavalent chromium compounds), peroxide compound (peroxide compound), Tollen reagent, persulfuric acid (persulfuric acid), oxygen (oxygen) or ozone (ozone), but not as limit, each oxygenant has different active oxygen ratios and different byproducts.In one embodiment, oxygenant is hydrogen peroxide (H
2O
2), its concentration is about 10% to 50% (weight percent), and is preferred, concentration can be greater than 30%, and for example 30% to 50%, so that best desulfuration efficiency to be provided.
Ionic liquid can be the solvent of the ion of any kind, for example the positively charged ion and the negatively charged ion that produce in solution of general salt.In one embodiment, ionic liquid contains nitrogenous organic cation and inorganic anion, and the melt temperature of preferred salt is lower than room temperature, makes at room temperature to be liquid state.For example, ionic liquid can be [trimethylammonium ammonia] [aluminum chloride] (Tri-Methylammonium Chloroaluminate, [TMAC] [AlCl
3]), [1-ethyl-3-Methylimidazole] [a tetrafluoro borate] (1-Ethyl-3-Methylimidazolium Tetrafluoroborate, [EMIM] [BF
4]), [1-butyl-3-Methylimidazole] [phosphofluoric acid] (1-Butyl-3-Methylimidazolium Hexafluorophosphate, [BMIM] [PF
6]), [1-butyl-3-Methylimidazole] [a tetrafluoro borate] (1-Butyl-3-Methylimidazolium Tetrafluoroborate, [BMIM] [BF
4]).With volume production, can use [1-butyl-3-Methylimidazole] [sodium octyl sulfate] (1-Butyl-3-Methylimidazolium Octyl Sulfate, [BMIM] [OcSO
4]) or [1-ethyl-3-Methylimidazole] [sulfovinate] (1-Ethyl-3-Methylimidazolium Ethyl Sulfate, [EMIM] [EtSO
4]).In another embodiment, the ionic liquid of solid type can be used, as 1,2,3-trimethylammonium Methylsulfate (1,2,3-Trimethylimidazolium methyl sulfate), 1,2,4-trimethylammonium pyrazoles Methylsulfate (1,2,4-Trimethylpyrazolium methylsulfate), 1-ethyl-2,3-dimethyl sulphide acetoacetic ester (1-Ethyl-2,3-dimethylimidazolium ethyl sulfate), 1-ethyl-3-Methylimidazole mesylate (1-Ethyl-3-methylimidazolium methanesulfonate) or 1,3-methylimidazole Methylsulfate (1,3-Dimethylimidazolium methyl sulfate).Before Medium diesel oil fuel, can be earlier the ionic liquid of these solid types be melted in hot water.
Acid catalyst can be any acid, preferably a kind of organic acid.In one embodiment, acid catalyst comprise acetic acid (acetic acid), trifluoroacetic acid (tri-fluoro acetic acid, TFA) or trichoroacetic acid(TCA) tri-chloro acetic acid, TCA).Perhaps, acid catalyst can comprise the mixture of above-mentioned acid, and to obtain better catalytic capability, for example, acid catalyst comprises 20% trifluoroacetic acid and 80% acetic acid (weight percent).In another embodiment, acid catalyst comprises the trichoroacetic acid(TCA) of 20%-50% trifluoroacetic acid, 10%-30% and the acetic acid of 40%-60%, for example, and 30% trifluoroacetic acid, 20% trichoroacetic acid(TCA) and 50% acetic acid.
It should be noted that the present invention do not need to add any consisting of phase-transferring agent (phase transfer agent, PTA).In known techniques, can add usually as four octyl group fluorochemicals (Tetraoctylammonium fluoride, TOAF) or four octyl chlorides (Tetraoctylammonium chloride, TOAC) consisting of phase-transferring agent of Denging is in solution.The present invention can effectively reduce cost of manufacture without any need for the practice of consisting of phase-transferring agent.Another one characteristics of the present invention are, in the process of mixing above-mentioned fuel, oxygenant, ionic liquid and acid catalyst, do not need to carry out the step of ultrasonic stirring, but desulfuration efficiency can keep identical or even greater than the known processing procedure that needs ultrasonic stirring.
Summed up the embodiment of above-mentioned first step: sulfurous fuels is transported in the container, with the acid catalyst that contains 30% trifluoroacetic acid (TFA), 20% trichoroacetic acid(TCA) (TCA) and 50% acetic acid, mix as hydrogen peroxide and the ionic liquid of oxygenant, but do not use consisting of phase-transferring agent and ultrasonic stirring.Table 1 shows a preferred implementation in the first step.
Table one
Second step is to use a kind of solid catalyst, and for example aluminum oxide (alumina) or acetonitrile (acetonitrile) and microporous crystalline titanosilicate (microporous crystalline titanium silicates) carry out desulfurization.Through first step and second step, the sulphur in the fuel 99.9% is removed.Table 2 has shown the desulfuration efficiency of a kind of method of desulfurization of fuels of the present invention, and it has comprised various fuel, as BP#6, JP-5, F-76 and valley oil.Method of desulfurization of fuels as shown in table 2, that the present invention is used, its desulfurization degree can reach 99.9%, has represented great sweetening power.
Table 2
The 3rd step of method of the present invention is ionic liquid and the acid catalyst that will reclaim.Recovery method of the present invention comprises: add one first solution to, for example deionized water (deionized water) adds in the ionic liquid with the ratio of 1:1 to 1:6, so that the organosulfur in the fuel (OCS) becomes fractional precipitation.After adding first solution, will contain the orange throw out of organosulfur again by centrifugal removal.In this step, about 90% organosulfur can be removed.
After removing throw out, then one second solution joins in the solion so that organosulfur is removed fully.In an embodiment, the ratio of second solution and ionic liquid is rough to be 1:1,1:2,1:5,1:10, or 1:20.In order to satisfy the requirement of extraction, second solution comprises following two restrictions, and the first, the second solution must not dissolve each other with ionic liquid; The second, the second solution can extract organosulfur (as sulfone) from ionic liquid.In one embodiment, second solution comprises 1-butanols (1-butanol), chloroform (chloroform), chlorobenzene (chlorobezene), ether (diethyl ether), ethyl acetate (diethyl acetate), normal heptane (heptane), hexane (hexane), triethylamine (triethyl amine) or toluene (toluene), but not as limit.In a preferred embodiment, second solution is chloroform or ethyl acetate, because the relatively low (chloroform: 61 ℃ of their fusing point; Ethyl acetate: 77 ℃), so in subsequent step, be removed easily.After adding second solution, original solion will form one second solution mutually and an ionic liquid mutually, an organosulfur at parent ion solution can be extracted into the second solution phase.Second solution can use the device as separating funnel to separate with ionic liquid mutually.Follow-up, the ionic liquid that separates is carried out a distillation processing procedure mutually, so that position organosulfur, acid catalyst and oxygenant therein removed the ionic liquid that can obtain regenerating.In one embodiment, through the extraction in three cycles, the organosulfur in the ionic liquid can be reduced to the degree that HPLC can't detect.Follow-up, the ionic liquid of reusable regeneration, for example the ionic liquid with these regeneration adds new fuel, oxygenant and acid catalyst (needing if having), use as the first part of preamble,
Please refer to Fig. 1, it illustrates the block schematic diagram of a continuous-flow system used in the present invention.As shown in Figure 1, in continuous-flow system, after ionic liquid, oxygenant and acid catalyst were incorporated into premixer (pre-mixer), through mixing, vacuum pump can be sent to these mixtures in the one on-mechanical mixing tank (non-mechanical mixer).Please refer to Fig. 2 and Fig. 3, illustrate is the synoptic diagram of a kind of on-mechanical mixing tank among the present invention.As shown in Figure 2, this on-mechanical mixing tank is a rectangular line style mixing tank (in-line mixer), and it comprises a hollow tube 300 and the inside prominent a plurality of protuberances 302 of tube wall, to form an irregular internal surface.When fuel, ionic liquid, oxygenant and acid catalyst circulate this hollow tube 300, by irregular internal surface, can increase reaction area and mix power, and then increase the speed of oxidizing reaction.Therefore in the present invention, do not need to use as hyperacoustic stirring system, and on-mechanical mixing tank of the present invention does not need electric device to drive yet.In one embodiment, as shown in Figure 3, more than one mixing tank series connection can be used, with further raising oxidation efficiency.
Then, refer again to Fig. 1, the on-mechanical mixing tank is sent the mixed solution of a part back to premixer, and the mixed solution of another part is delivered to a separator, for example is a whizzer.The ionic liquid that whizzer is separated and acid catalyst add first solution and second solution in regular turn, to recycle step as previously described.The ionic liquid that reclaims is introduced in the premixer, and in some cases, new ionic liquid, oxygenant or catalyzer can be re-supplied in the premixer.
On the other hand, whizzer sends the part of nonionic liquid to a retention tank, follow-up be resent to a fluidized-bed reactor (fluidized be reactor, FBR).Fluidized-bed reactor generally includes a bed of packings (packed bed) and a steel basin (stirring tank).Solution can enter from the bottom of groove, and at the top of steel basin the in good time product that removes.Include sweetening agent such as aluminum oxide, the fuel desulfuration of the oxidation that makes in the sulfuration bed bioreactor.Sweetening agent in the fluidized-bed reactor can reclaim and regenerate.Behind the sulfuration bed bioreactor, the fuel diesel output of final desulfurization.
As implied above, the invention provides a kind of method of desulfurization of fuels, be the ionic liquid that uses an on-mechanical mixing tank and recovery.Use ultrasonic stirring or other to spend the stirring means of high electric power compared to prior art, method of the present invention can have excellent desulfuration efficiency.Table 3 has been listed the desulfurization rate of different embodiment according to the subject invention.
Table 3
As shown in table 3, according to embodiment 1 and embodiment 2, do not use ultrasonic stirring and consisting of phase-transferring agent can obtain a higher desulfuration speed among the embodiment 2.When comparing embodiment 2 and embodiment 3, the concentration to 50% that increases hydrogen peroxide among the 3rd embodiment also can improve desulfurization rate.According to embodiment 4, revise the bitter desulfurization rate that further improves of catalyst concn.In addition, in embodiment 1, in the fuel [S atom]: [O atom] about 1:50 in the oxygenant, and in embodiment 2,3 and 4, [S atom]: [O atom] is about 1:10,1:10 and 1:7 respectively, especially very near contriver's ideal situation 1:2.Therefore, in the present invention, embodiment 2,3 and 4 provide suitable [S atom]: [O atom] ratio, in sweetening process, can raise the efficiency.
In addition, the invention provides a kind of method that reclaims ionic liquid and catalyzer.Please refer to Fig. 4 and Fig. 5, wherein Fig. 4 shows the nmr spectrum chart of an original ionic liquid, and Fig. 5 shows the nmr spectrum of the ionic liquid after the recycling.As Fig. 4 and shown in Figure 5, the ionic liquid of regeneration almost has identical composition combination with original ionic liquid.So it is effective can believing recovery method of the present invention.The contriver further finds, uses the ionic liquid of regenerating in first part, can promote the desulfuration efficiency of about 10%-50%.In addition, employed solvent in recycling step is to use deionized water as first solution, and its solution is obtained and is cheap, more can save the cost of processing procedure.
Another characteristics of the present invention are that temperature of reaction can at room temperature be carried out, and equally also can reach the same desulfuration efficiency.In prior art, reaction must for example be carried out under 70 ℃ to 100 ℃ the environment surpassing 70 ℃ usually.In the present embodiment, be under room temperature (30 ℃-50 ℃) and normal pressure (about 1 normal atmosphere), to carry out.
In sum, the invention provides a kind of more high-level efficiency and cost-effective method of desulfurization of fuels, this method comprises many improved features, for example uses the on-mechanical mixing tank and does not use that ultrasonic wave is mixed, ionic liquid, different oxidant concentration and the acid catalyst etc. of regeneration.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (20)
1. the method for a Desulphurization of fuels is characterized in that, comprises:
(a) with an oxidized, comprise and use an ionic liquid, an oxygenant and an acid catalyst;
(b) fuel after the oxidation is added a sweetening agent, to form a desulfurized fuel; And
(c) reclaim this ionic liquid, comprise the following step:
In through this ionic liquid of step (a), add one first solution;
After adding this first solution, add one second solution in this ionic liquid, to form one second solution mutually and an ionic liquid phase;
Remove this second solution phase; And
Remove at this first solution, this oxygenant and this acid catalyst of this solion in mutually, to obtain an ionic liquid that reclaims.
2. the method for Desulphurization of fuels according to claim 1 is characterized in that in step (c), this first solution is deionized water.
3. according to the method for claim 1 a described Desulphurization of fuels, it is characterized in that in step (c), add this first solution after, remove a throw out, and then add this second solution.
4. according to the method for claim 1 a described Desulphurization of fuels, it is characterized in that in step (c), this second solution comprises 1-butanols, chloroform, chlorobenzene, ether, ethyl acetate, normal heptane, hexane, triethylamine or toluene.
5. according to the method for claim 1 a described Desulphurization of fuels, it is characterized in that in step (c), remove the step at this first solution, this oxygenant and this acid catalyst of this solion in mutually, is by a distilation steps.
6. according to the method for claim 1 a described Desulphurization of fuels, it is characterized in that step (c) triplicate.
7. the method for a Desulphurization of fuels is characterized in that comprising:
(a) with an oxidized, comprise and use an ionic liquid, an oxygenant and an acid catalyst; And
(b) fuel after the oxidation is added a sweetening agent, forming a desulfurized fuel,
Wherein in step (a), do not use any consisting of phase-transferring agent.
8. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this consisting of phase-transferring agent comprises four octyl group fluorochemicals or four octyl chlorides.
9. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this ionic liquid comprises [trimethylammonium ammonia] [aluminum chloride], [1-ethyl-3-Methylimidazole] [a tetrafluoro borate], [1-butyl-3-Methylimidazole] [phosphofluoric acid], [1-butyl-3-Methylimidazole] [a tetrafluoro borate], [1-butyl-3-Methylimidazole] [sodium octyl sulfate] or [1-ethyl-3-Methylimidazole] [sulfovinate].
10. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this ionic liquid comprises 1,2,3-trimethylammonium Methylsulfate, 1,2,4-trimethylammonium pyrazoles Methylsulfate, 1-ethyl-2,3-dimethyl sulphide acetoacetic ester, 1-ethyl-3-Methylimidazole mesylate or 1,3-methylimidazole Methylsulfate.
11. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this oxygenant comprises the compound of hypohalite, chlorite, permanganate salt ammonium, cerous nitrate, hexavalent chromium compound, peroxide compound, Tollen reagent, persulfuric acid, oxygen or ozone.
12. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this oxygenant is hydrogen peroxide, and in step (a), the concentration of hydrogen peroxide is in fact between 30% to 50%.
13. according to the method for claim 7 a described Desulphurization of fuels, it is characterized in that this acid catalyst comprises acetic acid, trifluoroacetic acid or trichoroacetic acid(TCA).
14. according to the method for claim 13 a described Desulphurization of fuels, it is characterized in that in step (a), this acid catalyst comprises the trichoroacetic acid(TCA) of 20%-50% trifluoroacetic acid, 10%-30% and the acetic acid of 40%-60%.
15. according to the method for claim 7 a described Desulphurization of fuels, the method that it is characterized in that this Desulphurization of fuels is to carry out to the environment of 50 degree Celsius at 30 degree Celsius.
16. the method for a Desulphurization of fuels is characterized in that comprising:
(a) with an oxidized, comprise and use an ionic liquid, an oxygenant and an acid catalyst; And
(b) fuel after the oxidation is added a sweetening agent, forming a desulfurized fuel,
Wherein in step (a), do not use ultrasonic stirring.
17. according to the method for claim 16 a described Desulphurization of fuels, it is characterized in that in step (a), comprising use one on-mechanical mixing tank.
18. according to the method for claim 17 a described Desulphurization of fuels, it is characterized in that this on-mechanical mixing tank comprises a hollow tube and a plurality of protuberance is charged into to hollow tube.
19. according to the method for claim 17 a described Desulphurization of fuels, it is characterized in that this on-mechanical mixing tank comprises does not need power supply to drive.
20. according to the method for claim 16 a described Desulphurization of fuels, the method that it is characterized in that this Desulphurization of fuels is to carry out to the environment of 50 degree Celsius at 30 degree Celsius.
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| US13/760,009 US9127214B2 (en) | 2012-02-06 | 2013-02-05 | Fuel desulfurization method |
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