CN100529024C - Method for eliminating sulfur compound contained in fuel oil by catalytic oxidation of phase transition - Google Patents
Method for eliminating sulfur compound contained in fuel oil by catalytic oxidation of phase transition Download PDFInfo
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- CN100529024C CN100529024C CNB2007100617463A CN200710061746A CN100529024C CN 100529024 C CN100529024 C CN 100529024C CN B2007100617463 A CNB2007100617463 A CN B2007100617463A CN 200710061746 A CN200710061746 A CN 200710061746A CN 100529024 C CN100529024 C CN 100529024C
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- quaternary ammonium
- peroxyformic acid
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Abstract
This invention discloses a method for removing sulfur-containing compounds from fuel oil by phase-transfer catalytic oxidation. The method comprises: preparing six types of heteropolyacid quaternary ammonium salts as the phase-transfer catalysts from quaternary ammonium salts and phosphomolybdic acid/tungstophosphoric acid, mixing the phase-transfer catalysts, fuel oil, and peroxyformic acid oxidant (prepared from H2O2 and formic acid at a weight ratio of 3.5:(1-1.5)), reacting at 25-55 deg.C under ultrasonication for 1-2 h, and separating fuel oil and peroxyformic acid to obtain desulfurized fuel oil. The method avoids adsorption and extraction procedures due to the heteropolyacid quaternary ammonium salts phase-transfer catalysts, and has such advantages as simple process, and high reaction rate. The catalyst has such advantages as no toxicity and no pollution, and is recyclable and environmentally friendly.
Description
Technical field
The present invention relates to the method that a kind of phase transfer catalytic oxidation removes sulfocompound in the oil fuel, belong to petroleum chemical industry oil product refining techniques field.
Background technology
The high speed development of petroleum industry and automotive industry is that huge contribution has been made in social progress, but the severe corrosive SO that sulfocompound forms when burning in the oil fuel
2Deng discharging be to form the immediate cause that acid rain causes environmental pollution, also cause CO, NO simultaneously
xDeng increase.Producing the cleaning low sulphur fuel oil has become the task of top priority of oil refining industry.Sulphur content accounts for the 80-95% of gasoline total sulfur content in China's catalytic-cracked oil products.Therefore, carrying out the research of catalytic-cracked oil products desulfurization technology has great importance.At present, desulfurization of fuel oil method can be divided into two classes both at home and abroad: hydrogenating desulfurization and non-hydrogenating desulfurization, non-hydrogenating desulfurization comprise methods such as adsorption desulfurize, solvent extraction desulfurization, biological desulphurization and oxidation sweetening again.Wherein, oxidation desulfurizing method is with its processing condition gentleness, and cost is low, and oxidation products is a water-soluble sulfide, separates significant advantages such as easy, has caused people's very big concern.But the ubiquitous problem of disclosed oxidation desulfurizing method is that the reaction two-phase is not dissolved each other in the prior art, effective mixedness of aqueous phase oxidation agent and sulfocompound is relatively poor, make oxygenant and the sulfocompound can only be in the collision at the interface of water-organic phase, contact probability is little, speed of response slows down, and influences sweetening effectiveness.Since Starks in 1971 formally proposes " phase-transfer catalysis " notion and phase-transfer catalysis mechanism, caused people's extensive interest.It can make the heterogeneous homogeneous reaction that is converted into by self cationic surface activation, and fast reaction speed relaxes reaction conditions, simplifies the operation course, and reduces side reaction, improves selectivity, and does not need expensive anhydrous solvent or aprotic solvent.Therefore, based on the characteristics of problem that exists in the selective oxidation desulfurization and phase-transfer-catalyzed reactions, the exploitation phase transfer catalytic oxidation removes that the Technology of sulfocompound has important and practical meanings in the oil fuel.
Summary of the invention
The objective of the invention is at the oxygenant and the sulfocompound contact probability of sulfocompound method existence in the present selective oxidation removal oil fuel little, speed of reaction is slow, sweetening effectiveness difference and catalyzer are difficult to problems such as recycling and recovery, the method that provides a kind of phase transfer catalytic oxidation to remove sulfocompound in the oil fuel, thus realize the production that cleans of oil product.
Design of the present invention is such: the profit parents character of utilizing the heteropolyacid phase-transfer catalyst, can make the oxygenant and the sulfocompound in the organic phase that are present in water realize alternate transfer, thereby enlarge the contact area of reactant, accelerate speed of reaction, under the non-pressurized mitigation condition of room temperature, be materials such as strong polar sulfone, sulfoxide, vitriol with the selective oxidation of sulfur containing compounds in particular in the oil fuel, reach the purpose of deep desulfuration, simultaneously, the heteropolyacid phase-transfer catalyst can be realized reclaiming through simple filtering.The contriver on the basis of synthetic heteropolyacid quaternary ammonium salt phase transfer catalyst, systematic study heteropolyacid quaternary ammonium salt phase transfer catalytic oxidation remove the reaction process of sulfocompound in the oil fuel, optimized processing condition, realized the deep desulfuration of oil fuel.Method of the present invention is described as: under the ultrasonic wave condition, oil fuel and oxygenant peroxyformic acid are mixed in proportion, add an amount of phase-transfer catalyst heteropolyacid quaternary ammonium salt, under 25～55 ℃, reaction 1～2h separates oil fuel and peroxyformic acid, obtains oil fuel after the desulfurization;
In the method for the present invention, oil fuel is (0.5～5) with the mixed volume ratio of oxygenant peroxyformic acid: 1;
Peroxyformic acid is pressed mass ratio 3.5 by hydrogen peroxide and formic acid: (1～1.5) is formulated;
The add-on of phase-transfer catalyst is: in every 1mL reaction system the add-on of phase-transfer catalyst be 0.001～0.004 the gram, reaction system be oil fuel and oxygenant peroxyformic acid volume with.
Phase-transfer catalyst heteropolyacid quaternary ammonium salt synthetic method of the present invention is: the quaternary ammonium salt phase transfer catalyst aqueous solution is preheated to 40 ℃ in ultrasonic wave, slowly drip heteropolyacid (phospho-molybdic acid/phospho-wolframic acid) aqueous solution again, behind the reaction 2h, the room temperature ageing is spent the night, filter, obtain yellow powder shape solid heteropoly acid quaternary ammonium salt phase transfer catalyst.Totally six kinds of synthetic heteropolyacid quaternary ammonium salt phase transfer catalysts can be selected a kind of use arbitrarily, are listed as follows:
The boiling range of oil fuel is generally 60～350 ℃ among the present invention, comprises gasoline and diesel oil distillate.
The positively effect that the present invention obtains is: adopt nontoxic heteropolyacid quaternary ammonium salt phase transfer catalyst, avoided environmental pollution; Save absorption and extraction process, simplified processing step; The phase-transfer catalyst that employing can reuse has reduced reaction cost; Reaction times is shorter, helps industrial applications.
Embodiment
Following examples are used to illustrate the present invention, but these embodiment do not limit the present invention.
Embodiment 1
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 12mL catalytically cracked gasoline and 36mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-1 simultaneously, control reaction temperature is 40 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 11.76mL of 94.8 μ g/g, and desulfurization degree is 88%.
Embodiment 2
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 24mL catalytically cracked gasoline and 24mL are pressed 3.3: 1.5 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-2 simultaneously, control reaction temperature is 30 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 23.04mL of 7.9 μ g/g, and desulfurization degree is 99%.
Embodiment 3
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 36mL catalytically cracked gasoline and 12mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-3 simultaneously, temperature of reaction is 50 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 32.76mL of 55.2 μ g/g, desulfurization degree is 92%, heteropolyacid quaternary ammonium salt phase transfer catalyst after the use is after regeneration, be applied to desulfurization of fuel oil technology once more, obtaining sulphur content is the catalytic cracking diesel oil 32.4mL of 69 μ g/g, and desulfurization degree is 90%.
Embodiment 4
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 24mL catalytically cracked gasoline and 24mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.05g heteropolyacid quaternary ammonium salt phase transfer catalyst M-4 simultaneously, control reaction temperature is 40 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 23.76mL of 72.2 μ g/g, and desulfurization degree is 88%.
Embodiment 5
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 24mL catalytically cracked gasoline and 24mL are pressed 3.3: 1.5 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.15g heteropolyacid quaternary ammonium salt phase transfer catalyst M-5 simultaneously, control reaction temperature is 50 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 2h, obtaining sulphur content is the catalytic cracking diesel oil 22.32mL of 13.8 μ g/g, and desulfurization degree is 98%.
Embodiment 6
The sulphur content of catalytically cracked gasoline is 690 μ g/g, and boiling range is 60～200 ℃.
Under the ultrasonic wave condition, 24mL catalytically cracked gasoline and 24mL are pressed 3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-6 simultaneously, control reaction temperature is 30 ℃, separate catalytically cracked gasoline and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 23.28mL of 124.2 μ g/g, and desulfurization degree is 96%.
Embodiment 7
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 12mL catalytic cracking diesel oil and 36mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-1 simultaneously, temperature of reaction is 30 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 1h, obtaining sulphur content is the catalytic cracking diesel oil 11.16mL of 238.0 μ g/g, desulfurization degree is 83%, heteropolyacid quaternary ammonium salt phase transfer catalyst after the use is after regeneration, be applied to desulfurization of fuel oil technology once more, obtaining sulphur content is the catalytic cracking diesel oil 10.92mL of 252 μ g/g, and desulfurization degree is 82%.
Embodiment 8
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 24mL catalytic cracking diesel oil and 24mL are pressed 3: 1.5 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-2 simultaneously, temperature of reaction is 40 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 23.28mL of 28 μ g/g, and desulfurization degree is 98%.
Embodiment 9
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 36mL catalytic cracking diesel oil and 12mL are pressed 3.5: 1.5 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-3 simultaneously, control reaction temperature is 40 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 2h, obtaining sulphur content is the catalytic cracking diesel oil 32.4mL of 14 μ g/g, and desulfurization degree is 99%.
Embodiment 10
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 24mL catalytic cracking diesel oil and 24mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.05g heteropolyacid quaternary ammonium salt phase transfer catalyst M-4 simultaneously, control reaction temperature is 25 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 1h, obtaining sulphur content is the catalytic cracking diesel oil 23.76mL of 210.0 μ g/g, and desulfurization degree is 85%.
Embodiment 11
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 24mL catalytic cracking diesel oil and 24mL are pressed 3.3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.10g heteropolyacid quaternary ammonium salt phase transfer catalyst M-5 simultaneously, control reaction temperature is 40 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 23.28mL of 56 μ g/g, desulfurization degree is 96%, heteropolyacid quaternary ammonium salt phase transfer catalyst after the use is without regeneration, directly apply to desulfurization of fuel oil technology once more, obtaining sulphur content is the catalytic cracking diesel oil 22.08mL of 112 μ g/g, and desulfurization degree is 92%.
Embodiment 12
The sulphur content of catalytic cracking diesel oil is 1400 μ g/g, and boiling range is 180～350 ℃.
Under the ultrasonic wave condition, 24mL catalytic cracking diesel oil and 24mL are pressed 3: 1 formulated peroxyformic acid adding reactors of mass ratio by hydrogen peroxide and formic acid, add 0.15g heteropolyacid quaternary ammonium salt phase transfer catalyst M-6 simultaneously, control reaction temperature is 30 ℃, separate catalytic cracking diesel oil and peroxyformic acid behind the reaction 1.5h, obtaining sulphur content is the catalytic cracking diesel oil 20.64mL of 196 μ g/g, and desulfurization degree is 86%.
Claims (2)
1, a kind of phase transfer catalytic oxidation removes the method for sulfocompound in the oil fuel, it is characterized in that: under the ultrasonic wave condition, oil fuel is mixed with the oxygenant peroxyformic acid, add phase-transfer catalyst heteropolyacid quaternary ammonium salt, under 25～55 ℃, behind reaction 1～2h, separate oil fuel and peroxyformic acid, obtain oil fuel after the desulfurization;
Wherein, peroxyformic acid is pressed mass ratio 3.5 by hydrogen peroxide and formic acid: (1～1.5) is formulated;
Oil fuel is (0.5～5) with the mixed volume ratio of oxygenant peroxyformic acid: 1;
The add-on of phase-transfer catalyst is: the add-on 0.001～0.004g of phase-transfer catalyst in every 1mL reaction system;
Said phase-transfer catalyst heteropolyacid quaternary ammonium salt is a kind of in following:
[(C
2H
5)
4N]
3PMo
12O
40，[(C
4H
9)
4N]
3PMo
12O
40，[(CH
3)
3(C
16H
33)N]
3PMo
12O
40，[(C
2H
5)
4N]
3PW
12O
40，[(C
4H
9)
4N]
3PW
12O
40，[(CH
3)
3(C
16H
33)N]
3PW
12O
40。
2, by the described method of claim 1, it is characterized in that: the oil fuel boiling range is 60～350 ℃.
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| CNB2007100617463A CN100529024C (en) | 2007-04-26 | 2007-04-26 | Method for eliminating sulfur compound contained in fuel oil by catalytic oxidation of phase transition |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173179B (en) | 2007-10-24 | 2010-09-29 | 中国科学院大连化学物理研究所 | Catalyst for diesel oil oxidation distillation ultra-deepness desulfurization and desulfurization method |
| CN102311779A (en) * | 2011-08-22 | 2012-01-11 | 浙江工业大学 | Method of peroxyformic acid of gasoline oxidation extraction and desulfurization |
| CN103555366B (en) * | 2013-11-13 | 2015-10-28 | 河北科技大学 | A kind of method of catalytic oxidative desulfurization dibenzothiophene |
| CN104966780B (en) * | 2015-05-13 | 2017-11-24 | 吉林大学 | Surfactant cladding multi-metal oxygen cluster compound, preparation method and applications |
| CN108753408B (en) * | 2018-06-22 | 2023-12-19 | 山西焦煤集团有限责任公司 | Catalytic ozone liquid phase oxidation high sulfur coal desulfurization method |
| CN108753407A (en) * | 2018-06-22 | 2018-11-06 | 山西焦煤集团有限责任公司 | A kind of method of coal oxidation removing organic sulfur |
| CN110252413A (en) * | 2019-06-27 | 2019-09-20 | 石河子开发区汇智元科技有限责任公司 | One kind being used for C9 resin raw material oil oxidation desulfurization catalyst |
| RU2711756C1 (en) * | 2019-06-27 | 2020-01-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Method for catalytic cracking of vacuum gas oil |
| CN115532308B (en) * | 2021-06-29 | 2023-08-22 | 中石化南京化工研究院有限公司 | Phase transfer catalyst for removing sulfur-containing salt, and sulfur-containing salt removing method and application thereof |
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