CN102212383B - Application method of ionic liquid for removing sulfur from oils - Google Patents
Application method of ionic liquid for removing sulfur from oils Download PDFInfo
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- CN102212383B CN102212383B CN 201010590210 CN201010590210A CN102212383B CN 102212383 B CN102212383 B CN 102212383B CN 201010590210 CN201010590210 CN 201010590210 CN 201010590210 A CN201010590210 A CN 201010590210A CN 102212383 B CN102212383 B CN 102212383B
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Abstract
The invention relates to an application method of an ionic liquid for removing sulfur from oils. The method comprises the following steps: dissolving chloroalkyl carboxylic acid solid in deionized water and adding pyridine, fully washing with ethyl acetate, carrying out vacuum drying on the synthesized product and then dissolving into the deionized water; slowly dropwise adding concentrated sulfuric acid or concentrated phosphoric acid so as to prepare a pyridine salt ionic liquid for the desulfuration of the oils; adding the ionic liquid and imitated oils containing the sulfur content of 1000ppm, stirring and heating; adding an aqueous hydrogen peroxide solution, cooling to room temperature, and standing for layering, wherein desulfured oils are on the upper layer, carrying out rotary evaporation and reextraction on the ionic liquid on the lower layer so as to respectively achieve dehydration and separation of sulfone compounds, and carrying out vacuum drying so that the ionic liquid can be recycled. By using the method, the defects that the ionic liquid is large in dosage, high in cost and is difficult to meet deep desulfuration are overcome. The method can be used for synthesizing functionalized pyridine salt ionic liquids and used for oil oxidation/extraction deep desulfuration, the dosage of an oxidant is less, desulfuration efficiency is high, the ionic liquid can be recycled, the yield of the oils is high, cost is low, and environment is not polluted.
Description
Technical field
The present invention relates to oil product desulfurization method, particularly ionic liquid is for oil product desulfurization method.
Background technology
In oil fuel, S-contained substance can generate sulfur oxide SOx when high-temp combustion, and environment and human health are caused to very big harm.Along with the enhancing of people's environmental consciousness and the raising of vehicle fuel exhaust emission standard, world is increasingly strict to the restriction of fuel oil sulphur content, produce and use super low sulfur oil fuel imperative, and traditional sulfur method is difficult to reach the requirement of deep desulfuration.Therefore, ionic liquid is the eco-friendly deep desulfuration technology with industrialization development prospect newly developed in recent years for desulfurizing oil.
Ionic liquid be by positively charged positively charged ion and electronegative negatively charged ion, formed be the salt of liquid state near room temperature, with conventional organic solvents, compare, ionic liquid solubilized polarity and nonpolar organic and inorganic thing, almost there is no vapour pressure, easily separated, pollution-free, thermostability is high, chemical stability is good, reusable, and zwitterion that can be different by composite design regulates its physical and chemical performance, to meet specific application demand, ionic liquid is considered to have the green solvent of broad prospect of application.
Before the present invention, ionic liquid is for desulfurizing oil, study and apply more be using ionic liquid only as extraction agent, directly extract in oil product S-contained substance as thiophene, thionaphthene, dibenzothiophene etc.But directly its one way desulfurization degree of abstraction desulfurization is low, the ionic liquid consumption is large, and cost is high, and is difficult to meet the requirement of deep desulfuration.And the higher pyridine salt ionic liquid of catalytic activity is used for oil oxidation/extraction deep desulfuration, not only can avoid high energy consumption and the high pollution of in the conventional oxidation desulphurization reaction, using organic acid catalyst to cause, environmentally friendly, and can be by sulfoxide that oxidizing reaction generates, the timely extracting and separating of sulfone class sulphur oxidation products to ionic liquid, therefore there is better sweetening effectiveness than the direct abstraction desulfurization of ionic liquid, can obtain the super low sulfur clear gusoline.
Summary of the invention
The object of the invention is that pyridine synthesis salt ionic liquid is for oil oxidation/extraction deep desulfuration, proposes the eco-friendly desulfurization technology with industrialization development prospect.
Technical scheme of the present invention comprises the following steps:
(1) alkyl chloride yl carboxylic acid solid is dissolved in deionized water, the aqueous solution that the formation mass percent concentration is 35.0～40.0%, add pyridine, and under the ultrasonic field effect, after reaction, rotary evaporation removes water and excess pyridine, and fully washs by ethyl acetate; Above-mentioned synthetic product is dissolved in deionized water and forms the solution that mass percent concentration is 50.0～55.0% after vacuum-drying, slowly drip the vitriol oil or strong phosphoric acid under the ultrasonic field effect, after reaction finishes, rotary evaporation is except anhydrating and hydrogenchloride, make desulfurizing oil and react pyridine salt ionic liquid used, vacuum-drying is standby;
(2) adding the simulation oil product that described ionic liquid and sulphur content are 1000ppm (in oil fuel representational sulfide dibenzothiophene be dissolved in octane formulated) in reaction vessel, be warming up to 50～70 ℃ under magnetic agitation, add the aqueous hydrogen peroxide solution that mass percent concentration is 30%～35%, reaction is cooled to room temperature after finishing, stratification, upper strata is the desulfurization oil product, gas Chromatographic Determination sulphur content after anhydrous sodium sulfate drying, lower floor's ionic liquid can be recycled with stripping after separating sulfone compound vacuum-drying through rotary evaporation dehydration.
In above-mentioned steps (1), its cationic branched-chain of synthesized pyridine salt ionic liquid is carboxyalkyl (CH
2cOOH or-CH
2cH
2cOOH), negatively charged ion is strongly-acid bisulfate ion or dihydrogen phosphate;
In above-mentioned steps (1), the mol ratio of alkyl chloride yl carboxylic acid and pyridine and the vitriol oil or strong phosphoric acid is 1: 1.1: 1～1: 1.5: 1;
In above-mentioned steps (1), supersound process frequency used is 40～60kHz, and power is 350～500W, i.e. 2800～4000W/m
2, the ultrasonication time is 20～60min;
Adding ionic liquid and simulation oil product volume ratio in above-mentioned steps (2) is 1: 1.5～4;
Adding 30% aqueous hydrogen peroxide solution and simulation oil product volume ratio in above-mentioned steps (2) is 1: 50～70.
The present invention synthesizes the functionalization pyridine salt ionic liquid of high catalytic activity under ultrasound-enhanced effect and, for oil oxidation/extraction deep desulfuration, not only the oxygenant consumption is few, and desulfurization degree is high, and ionic liquid can be recycled, the oil product yield is high, and cost is low, free from environmental pollution.Therefore pyridine salt ionic liquid has formed the eco-friendly desulfurization technology with industrialization development prospect for the method for oil oxidation/extraction deep desulfuration, can produce higher economic benefit and social benefit.
Embodiment:
Embodiment 1:
106.7g Mono Chloro Acetic Acid solid is dissolved in the 200mL deionized water, adds the 100mL pyridine, react 30min (20-40min) under the ultrasonic field effect of frequency 60kHz, power 500W, rotary evaporation removes water and excess pyridine, and fully washs by ethyl acetate; Above-mentioned synthetic product is dissolved in after vacuum-drying in the deionized water of 200mL, slowly drip the vitriol oil that the 62mL mass percent concentration is 98% under identical ultrasonic field effect, reaction 30min (20-40min), after reaction finishes, rotary evaporation, except anhydrating and hydrogenchloride, makes desulfurizing oil and reacts pyridine salt ionic liquid [CH used
3cOOHPy] HSO
4, vacuum-drying is standby.
Accurately take the 1.0325g dibenzothiophene and be dissolved in octane and be settled to 250mL, the simulation oil product that to be mixed with sulphur content be 1000ppm.
Add the above-mentioned pyridine salt of 50mL ionic liquid [CH in reaction vessel
3cOOHPy] HSO
4with the above-mentioned simulation oil product of 100mL, be warming up to 60 ℃ (50-70 ℃) under magnetic agitation, add the aqueous hydrogen peroxide solution that the 1.8mL mass percent concentration is 30%, reaction 70min (60-80min); Reaction is cooled to room temperature after finishing, stratification, and getting upper strata desulfurization oil product its sulphur content of gas Chromatographic Determination after anhydrous sodium sulfate drying is 2.7ppm, desulfurization degree is 99.7%; Lower floor's ionic liquid can be recycled with stripping after separating sulfone compound vacuum-drying through rotary evaporation dehydration.
Embodiment 2:
Add pyridine salt ionic liquid described in 25mL embodiment 1 and 100mL simulation oil product in reaction vessel, all the other operate with embodiment 1, and the desulfurization oil product is 31.8ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 96.8%.
Embodiment 3:
Add pyridine salt ionic liquid described in 50mL embodiment 1 and 100mL simulation oil product in reaction vessel, be warming up to 60 ℃ under magnetic agitation, add the aqueous hydrogen peroxide solution that the 1.5mL mass percent concentration is 30%, all the other operations are with embodiment 1, the desulfurization oil product is 22.3ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 97.8%.
Embodiment 4:
All the other operations, with embodiment 1, only will slowly drip the sulfuric acid that the 62mL mass percent concentration is 98% and change the phosphoric acid that slow dropping 76.3mL mass percent concentration is 85% into, make desulfurizing oil and react pyridine salt ionic liquid [CH used
3cOOHPy] H
2pO
4, vacuum-drying is standby.
Add the above-mentioned pyridine salt of 50mL ionic liquid [CH in reaction vessel
3cOOHPy] H
2pO
4with 100mL simulation oil product, all the other operate with embodiment 1, and the desulfurization oil product is 27.8ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 97.2%.
Embodiment 5:
Add the ionic liquid after recycling and 100mL simulation oil product in 50mL embodiment 1 in reaction vessel, all the other operate with embodiment 1, and the desulfurization oil product is 15.2ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 98.5%.
Comparative analysis example 1:
106.7g Mono Chloro Acetic Acid solid is dissolved in the 200mL deionized water, add the 100mL pyridine, react 30min under the ultrasonic field effect of frequency 60kHz, power 500W, rotary evaporation removes water and excess pyridine, and fully wash by ethyl acetate, make desulfurizing oil and react pyridine salt ionic liquid [CH used
3cOOHPy] Cl, vacuum-drying is standby.
Add the above-mentioned ionic liquid of 50mL and 100mL simulation oil product in reaction vessel, all the other operate with embodiment 1, and the desulfurization oil product is 708.4ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 29.2%.Comparative analysis example 2:
108.4g Mono Chloro Acetic Acid solid is dissolved in the 200mL deionized water, add 100mL N-Methylimidazole, react 30min under the ultrasonic field effect of frequency 60kHz, power 500W, rotary evaporation removes water and excessive N-Methylimidazole, all the other operations, with embodiment 1, make desulfurizing oil and react imidazole salt ionic liquid [CH used
3cOOHMim] HSO
4, vacuum-drying is standby.
Add the above-mentioned ionic liquid of 50mL and 100mL simulation oil product in reaction vessel, all the other operate with embodiment 1, and the desulfurization oil product is 82.9ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 91.7%.
Comparative analysis example 3:
Add 95mL monobromethane and 100mL pyridine in the 200mL hexanaphthene, 64 ℃ of lower stirring reaction 4h, generate a large amount of white solid product, is cooled to room temperature, filters and fully wash by ethyl acetate; Above-mentioned synthetic product is dissolved in 200mL methyl alcohol after vacuum-drying, adds the 138g sodium pyrosulfate, stirring reaction 4h under normal temperature, after reaction finishes, rotary evaporation is except desolventizing, and filtration gained filtrate is desulfurizing oil and reacts pyridine salt ionic liquid [CH used
2cH
3py] HSO
4, vacuum-drying is standby.
Add the above-mentioned ionic liquid of 50mL and 100mL simulation oil product in reaction vessel, all the other operate with embodiment 1, and the desulfurization oil product is 644.3ppm through its sulphur content of gas Chromatographic Determination, and desulfurization degree is 35.6%.
From above-mentioned comparison example, when preparing oil oxidation/abstraction desulfurization and react ionic liquid used, if use other zwitterion combination instead, the desulfurizing oil rate obviously reduces.
Claims (6)
1. ionic liquid, for the method for desulfurizing oil, is characterized in that comprising the following steps:
(1) alkyl chloride yl carboxylic acid solid is dissolved in deionized water, the aqueous solution that the formation mass percent concentration is 35.0～40.0%, add pyridine, and under the ultrasonic field effect, after reaction, rotary evaporation removes water and excess pyridine, and fully washs by ethyl acetate; Above-mentioned synthetic product is dissolved in deionized water and forms the solution that mass percent concentration is 50.0～55.0% after vacuum-drying, slowly drip the vitriol oil or strong phosphoric acid under the ultrasonic field effect, after reaction finishes, rotary evaporation is except anhydrating and hydrogenchloride, make desulfurizing oil and react pyridine salt ionic liquid used, vacuum-drying is standby;
(2) add the simulation oil product that described ionic liquid and sulphur content are 1000ppm in reaction vessel, it is formulated that this simulation oil product representational sulfide dibenzothiophene in oil fuel is dissolved in octane, be warming up to 50～70 ℃ under magnetic agitation, add the aqueous hydrogen peroxide solution that mass percent concentration is 30%～35%, reaction is cooled to room temperature after finishing, stratification, upper strata is the desulfurization oil product, gas Chromatographic Determination sulphur content after anhydrous sodium sulfate drying, lower floor's ionic liquid can be recycled with stripping after separating sulfone compound vacuum-drying through rotary evaporation dehydration.
2. ionic liquid, for the method for desulfurizing oil, is characterized in that in synthesized pyridine salt ionic liquid, cationic branched-chain is carboxyalkyl according to claim 1, and described carboxyalkyl is-CH
2cOOH or-CH
2cH
2cOOH, negatively charged ion is strongly-acid bisulfate ion or dihydrogen phosphate.
3. ionic liquid is for the method for desulfurizing oil according to claim 1, and the mol ratio that it is characterized in that alkyl chloride yl carboxylic acid and pyridine and the vitriol oil or strong phosphoric acid is 1: 1.1: 1～1: 1.5: 1.
4. ionic liquid, for the method for desulfurizing oil, is characterized in that supersound process frequency used is 40～60kHz according to claim 1, and power is 350～500W, i.e. 2800～4000W/m
2, the ultrasonication time is 20～60min.
5. ionic liquid, for the method for desulfurizing oil, is characterized in that added ionic liquid and simulation oil product volume ratio are 1: 1.5～4 according to claim 1.
6. ionic liquid, for the method for desulfurizing oil, is characterized in that add, 30% aqueous hydrogen peroxide solution was 1: 50～70 with simulation oil product volume ratio according to claim 1.
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|---|---|---|---|
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| CN102690676A (en) * | 2012-05-14 | 2012-09-26 | 辽宁大学 | FCC (fluid catalytic cracking) gasoline oxidation desulfurization method by utilizing ionic liquids |
| CN105327689B (en) * | 2015-10-16 | 2018-06-22 | 华南理工大学 | A kind of preparation and its application of the molecular sieve gasoline desulfurizer of loading functional ionic liquid |
| CN105778980A (en) * | 2016-02-28 | 2016-07-20 | 辽宁石油化工大学 | Method for regenerating hydrophilic type ionic liquid desulfurizing agent through reverse extraction |
| CN107892940A (en) * | 2017-12-01 | 2018-04-10 | 河南科技大学 | A kind of method that persulfate of fluid coupling containing cobalt ions carries out desulfurizing oil |
| CN114249474B (en) * | 2020-09-22 | 2024-09-10 | 万华化学集团股份有限公司 | Process for removing nitrophenol organic matters in wastewater |
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| CN1827747A (en) * | 2006-04-03 | 2006-09-06 | 中国石油大学(北京) | Diesel oil coupled desulfurization method |
| JP2010215737A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method of purifying hydrocarbon oil by desulfurization or denitrification |
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| MX2008006731A (en) * | 2008-05-26 | 2009-11-26 | Mexicano Inst Petrol | Desulfurization of hydrocarbons by ionic liquids and preparation of ionic liquids. |
| US20100270211A1 (en) * | 2009-04-27 | 2010-10-28 | Saudi Arabian Oil Company | Desulfurization and denitrogenation with ionic liquids and metal ion systems |
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| CN1827747A (en) * | 2006-04-03 | 2006-09-06 | 中国石油大学(北京) | Diesel oil coupled desulfurization method |
| JP2010215737A (en) * | 2009-03-13 | 2010-09-30 | Idemitsu Kosan Co Ltd | Method of purifying hydrocarbon oil by desulfurization or denitrification |
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