CN101012390B - Method of realizing oil desulfuration by TiO2 catalyzed oxidation - Google Patents
Method of realizing oil desulfuration by TiO2 catalyzed oxidation Download PDFInfo
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- CN101012390B CN101012390B CN2007100635122A CN200710063512A CN101012390B CN 101012390 B CN101012390 B CN 101012390B CN 2007100635122 A CN2007100635122 A CN 2007100635122A CN 200710063512 A CN200710063512 A CN 200710063512A CN 101012390 B CN101012390 B CN 101012390B
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Abstract
The invention discloses desulfurizing method catalyzed and oxidized by TiO2 in the chemical technical domain, which comprises the following steps: adopting phosphotungstic acid as catalyst and STAB as porous agent; blending butyl titanate, STAB and anhydrous alcohol evenly in the phosphotungstic acid solution; adding deionized water; rotating to evaporate; drying; sintering under 500 deg.c for 3h; synthesizing TiO2 molecular sieve; adding TiO2 molecular sieve into DBT-octane solution; heating; adding H2O2 to oxidize; washing; recycling catalyst.
Description
Technical field
The present invention relates to a kind of TiO
2Catalyzed oxidation is realized the method for desulfurizing oil, is specifically related to a kind of big-pore mesoporous TiO
2The catalytic oxidation that synthesizes and use it for oil product of molecular sieve, the deep desulfuration of realization oil product belongs to technical field of chemistry and chemical engineering
Background technology
Along with the enhancing of science and technology development and people's environmental protection consciousness, the pollution that vehicle exhaust brought has become the focus that people pay close attention to gradually, and producing clean fuel will be the general trend of future development.National governments and petro-chemical corporation are all strengthening restriction aspect the oil sulphur content over past ten years.In the face of the restriction of the oil product sulphur content of increasingly stringent and the market great demand to the low-sulfur clean fuel oil, the deep desulfuration of oil product becomes the focus of research.Hydrogenating desulfurization is an important channel that reduces sulphur content in the oil, this technical development early, technology is comparatively ripe, most refineries adopt this method to handle catalytically cracked gasoline, sulphur in the catalytically cracked gasoline depends on the content of the sulphur compound in the charging, the petroleum refining industry of China has formed the technical process based on catalytic cracking for a long time, and the sulphur content height removes difficulty and cost height.Sulphur in the diesel oil mainly exists with the thiophene form, and wherein benzo and dibenzothiophene account for more than 70% of thiophene-based again, and these many penthienate stability are extremely strong, and hydrogenating desulfurization is difficult to remove.Carry out gasoline/diesel deep desulfurization research, reduction sulfur content in oil products, raising oil quality are had great importance.
The selective oxidation of sulfide is to have much prospect but a problem of very challenging property, and containing the oxidation of Ti molecular sieve catalytic is a more oxidation system of Recent study, but has some problems, as: the oxidant consumption amount is big, security is difficult to ensure; Long reaction time, process cost height; The condition harshness needs ultraviolet excitation that light-catalyzed reaction could take place.
Summary of the invention
The present invention be intended to propose a kind of easy, cheap, effectively realize the novel method of oil product deep desulfuration.
A kind of TiO
2Catalyzed oxidation is realized the method for desulfurizing oil, and this method comprises the steps:
1) mesoporous TiO
2Synthesizing of molecular sieve: 3.6g tetrabutyl titanate, STAB and dehydrated alcohol are mixed according to certain mass, add the aqueous solution of certain volume phospho-wolframic acid, add deionized water behind the stirring 3h, continue to stir 2h.Then mixture is taken out rotary evaporation, washing, drying, 500 ℃ of roastings.Wherein the mass ratio of tetrabutyl titanate and dehydrated alcohol is 1: 7; The phosphotungstic acid aqueous solution concentration of using is 0.15M; The mol ratio of phospho-wolframic acid and STAB is 1: 1; The volume ratio of phosphotungstic acid aqueous solution and deionized water is 0.96: 10; Roasting time is 3h.The mesoporous TiO of aforesaid method synthetic
2Molecular sieve has higher specific surface area, structurally ordered, has satisfactory stability.
2) with 0.1gTiO
2Molecular sieve joins in the DBT-octane mixing solutions of specific concentrations, treats that temperature is elevated to (70 ℃, 80 ℃) behind the design temperature, stirs to add 1mlH down
2O
2(30%, wt), oxidizing reaction begins.Reaction is separated after finishing, and takes out upper oil phase, with the content of gas chromatographic analysis DBT.
3) product is cooled to room temperature, centrifugation after the reaction.The water evaporation drying obtains catalyst solid, and surface adsorption has the solid sulfone, thereby sulfone class material wash-out can be used catalyst recirculation by water washing.
The present invention: (1) is catalyzer with the phospho-wolframic acid, and octadecyl trimethylammonium bromide (STAB) is a pore-creating agent, has synthesized that specific surface area is big, the uniform mesoporous TiO in aperture
2Molecular screen material; (2) be catalyzer with this molecular sieve, H
2O
2Be oxygenant, by the active catalytic of molecular sieve, with the organic sulfide catalyzed oxidations such as (DBT) of the dibenzothiophene in the oil phase; (3) the sulfone class product of Sheng Chenging is transferred to water by the extraction of water.Utilize this technology that the simulated system of DBT-octane is experimentized, obtained good effect, the DBT starting point concentration is that the solution of 300ppm can be realized 98% transformation efficiency in 2min.This process oxygenant consumption is few, and profit is in a ratio of 50: 1; Catalyst preparation process is simple and reusable, the economy height; Technological process is simple and safe, easily realizes industrialization.
Embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1:
3.6g tetrabutyl titanate, STAB and dehydrated alcohol are mixed according to certain mass, add the aqueous solution of certain volume phospho-wolframic acid, add deionized water behind the stirring 3h, continue to stir 2h.Then mixture is taken out rotary evaporation, washing, drying, 500 ℃ of roastings.Wherein the mass ratio of tetrabutyl titanate and dehydrated alcohol is 1: 7; The phosphotungstic acid aqueous solution concentration of using is 0.15M; The mol ratio of phospho-wolframic acid and STAB is 1: 1; The volume ratio of phosphotungstic acid aqueous solution and deionized water is 0.96: 10; Roasting time is 3h.Get the above-mentioned molecular sieve 0.1g that obtains, joining 50ml DBT initial content is in the octane solution of 300ppm, is warming up to 70 ℃, stirs to add 1mlH down
2O
2(30%, wt), begin reaction.Reaction finishes the back centrifugation, obtains upper organic phase, through gas chromatographic analysis, behind the reaction 2min in the octane solution content of DBT reduce to 5ppm, transformation efficiency reaches more than 98%.
Embodiment 2:
3.6g tetrabutyl titanate, STAB and dehydrated alcohol are mixed according to certain mass, add the aqueous solution of certain volume phospho-wolframic acid, add deionized water behind the stirring 3h, continue to stir 2h.Then mixture is taken out rotary evaporation, washing, drying, 500 ℃ of roastings.Wherein the mass ratio of tetrabutyl titanate and dehydrated alcohol is 1: 7; The phosphotungstic acid aqueous solution concentration of using is 0.15M; The mol ratio of phospho-wolframic acid and STAB is 1: 1; The volume ratio of phosphotungstic acid aqueous solution and deionized water is 0.96: 10; Roasting time is 3h.Get the above-mentioned molecular sieve 0.1g that obtains, joining 50ml DBT initial content is in the octane solution of 500ppm, is warming up to 70 ℃, stirs to add 1mlH down
2O
2(30%, wt), begin reaction.Reaction finishes the back centrifugation, obtains upper organic phase, through gas chromatographic analysis, behind the reaction 4min in the octane solution content of DBT reduce to below the 5ppm, transformation efficiency is 99%.
Embodiment 3:
3.6g tetrabutyl titanate, STAB and dehydrated alcohol are mixed according to certain mass, add the aqueous solution of certain volume phospho-wolframic acid, add deionized water behind the stirring 3h, continue to stir 2h.Then mixture is taken out rotary evaporation, washing, drying, 500 ℃ of roastings.Wherein the mass ratio of tetrabutyl titanate and dehydrated alcohol is 1: 7; The phosphotungstic acid aqueous solution concentration of using is 0.15M; The mol ratio of phospho-wolframic acid and STAB is 1: 1; The volume ratio of phosphotungstic acid aqueous solution and deionized water is 0.96: 10; Roasting time is 3h.Get the above-mentioned molecular sieve 0.1g that obtains, joining 50ml DBT initial content is in the octane solution of 3000ppm, is warming up to 80 ℃, stirs to add 1mlH down
2O
2(30%, wt), begin reaction.Reaction finishes the back centrifugation, obtains upper organic phase, through gas chromatographic analysis, behind the reaction 10min in the octane solution content of DBT reduce to 1100ppm, transformation efficiency is 63%.
Claims (1)
1. TiO
2Catalyzed oxidation is realized the method for desulfurizing oil, it is characterized in that this method comprises the steps:
1) mesoporous TiO
2Synthesizing of molecular sieve
Tetrabutyl titanate, octadecyl trimethylammonium bromide and dehydrated alcohol are mixed according to mass ratio, join in the aqueous solution of phospho-wolframic acid, stir and add deionized water after 3 hours, continue to stir 2 hours; Then mixture is taken out rotary evaporation, washing, drying, 500 ℃ of roastings 3 hours, synthesising mesoporous TiO
2Molecular sieve;
The mass ratio of described tetrabutyl titanate and dehydrated alcohol is 1: 7;
The mol ratio of described phospho-wolframic acid and octadecyl trimethylammonium bromide is 1: 1; Described phosphotungstic acid aqueous solution concentration is 0.15M; The volume ratio of phosphotungstic acid aqueous solution and deionized water is 0.96: 10;
2) by every 0.1g synthetic TiO
2Molecular sieve is with step 1) synthetic TiO
2Molecular sieve, join 50ml dibenzothiophene initial content and be 300,500 or the octane solution of 3000ppm in, treat that temperature is elevated to 70 ℃ or 80 ℃ of temperature after, stir and add H down
2O
2(30%, wt), TiO
2Molecular sieve and H
2O
2The ratio that adds is 0.1g: 1ml;
Oxidizing reaction begins; Reaction is separated after finishing, and takes out upper oil phase, realizes desulfurizing oil;
3) after the 2nd) the step reaction finishes, product is cooled to room temperature, centrifugation, the water evaporation drying obtains catalyst solid, and this catalyst solid surface adsorption has the solid sulfone, by water washing sulfone class material wash-out is used catalyst recirculation.
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|---|---|---|---|
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| CN101012390B true CN101012390B (en) | 2010-09-29 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173180B (en) * | 2007-09-12 | 2011-08-03 | 哈尔滨工程大学 | Phosphor and tungsten hetero-multi-quaternary ammonium salt desulfurizing agent and preparation method thereof |
| CN103275755A (en) * | 2013-05-24 | 2013-09-04 | 湖南大学 | Method for removing dibenzothiophene in oil through catalytic oxidation |
| CN104087335B (en) * | 2014-07-21 | 2015-12-30 | 青岛科技大学 | A kind of method removing dibenzothiophene in simulation fuel oil without catalysis co-oxidation |
| CN105038840B (en) * | 2015-09-09 | 2016-10-05 | 哈尔滨工业大学 | The method of thiophene sulfocompounds in a kind of homogeneous catalytic oxidation removing oil product |
| CN105694950B (en) * | 2016-01-29 | 2020-03-06 | 孙雪妮 | Photocatalytic real-time liquid phase adsorption desulfurization method |
| CN109589956B (en) * | 2018-12-26 | 2021-11-23 | 江苏大学 | Preparation method and application of defect-rich metal oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004015030A1 (en) * | 2002-08-07 | 2004-02-19 | Consejo Superior De Investigaciones Cientificas | Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions |
| CN1683476A (en) * | 2005-03-11 | 2005-10-19 | 清华大学 | Method for desulfurizing oil by catalytic oxidation and extracting and separating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004015030A1 (en) * | 2002-08-07 | 2004-02-19 | Consejo Superior De Investigaciones Cientificas | Method of oxidising mercaptans, thiophenic compounds and derivatives thereof in petrol, kerosene and diesel fractions |
| CN1683476A (en) * | 2005-03-11 | 2005-10-19 | 清华大学 | Method for desulfurizing oil by catalytic oxidation and extracting and separating |
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