CN105368492A - High-efficiency and environmental-friendly gasoline desulphurization method - Google Patents
High-efficiency and environmental-friendly gasoline desulphurization method Download PDFInfo
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- CN105368492A CN105368492A CN201410420183.2A CN201410420183A CN105368492A CN 105368492 A CN105368492 A CN 105368492A CN 201410420183 A CN201410420183 A CN 201410420183A CN 105368492 A CN105368492 A CN 105368492A
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Abstract
The invention discloses a high-efficiency and environmental-friendly gasoline desulphurization method. The method is characterized by including the following steps: (1) performing preliminary desulphurization: preparing an ionic liquid; (2) performing oxidation desulphurization: filling a reactor with oxygen, adding dibenzothiophene, stirring the mixture with a magnetic stirrer; (3) performing filtration to collect crystals; (4) preparing an active carbon adsorption plate: adding active carbon into a alkali liquor, passing ozone gas with stirring; and (5) sprinkling the filtrate prepared by step (3) to the prepared active carbon adsorption plate in a certain flow rate, performing liquid vacuum distillation, and recycling the desulfurized gasoline. The preliminary desulfurization rate reaches over 30%, and the additional product dibenzothiophene sulfone is obtained in desulphurization. The desulphurization method improves the adsorption capacity of the sulfide in the fuel oil, has high desulphurization efficiency and convenient operation, and is safe and without pollution.
Description
Technical field
The invention belongs to chemical desulfurization technical field, be specifically related to a kind of gasoline high-efficiency environment friendly sulfur method.
Background technology
Gasoline outward appearance is transparent liquid, mainly by C4 ~ C10 each race hydrocarbon composition, there are higher octane value and excellent anti-knocking property, for the vaporizer gasoline engine of high compression ratio, along with the continuous increase of gasoline consumption in global range, the harm of environment is also on the rise.The SOx of gasoline combustion discharge forms one of acid rain, the important factor causing topsoil.For meeting the international competitiveness of environmental requirement and raising China oil product, carrying out the research of gasoline desulfur technology, becoming the task of top priority.
Along with people are to the pay attention to day by day of environment protection, to also more and more stricter as the restriction of sulphur content in the light hydrocarbon of fuel.State IV gasoline standard of current domestic application, require that sulphur content is less than 50 μ g/g, mercaptans content is less than 10 μ g/g, and the following enforcement being less than " sweet gasoline (ULSG) " standard of 10 μ g/g along with content of sulfur in gasoline, in gasoline, total sulfur and mercaptan sulfur content also require further reduction.
In prior art, general employing hydrodesulfurizationprocess process removes the sulfide in catalytically cracked gasoline.Although the sulfide in hydrogenation technique energy effective elimination gasoline, also can, by olefin component hydrotreated lube base oil higher for octane value in gasoline, cause gasoline octane rating to lose larger simultaneously.In current existing non-hydrodesulfurization, the operational condition of oxidation sweetening is relatively gentle, facility investment is lower, and oxidation sweetening more easily removes in hydrogenating desulfurization, be difficult to removal thionaphthene and dibenzothiophene class sulfide.Therefore, how to produce a kind of gasoline high-efficiency environment friendly sulfur method, to obtain the gasoline products that sulphur content and uprising figure penalties reduce further, have important practical significance.
Summary of the invention
For the defect existed in prior art, the object of the present invention is to provide a kind of gasoline high-efficiency environment friendly sulfur method, preliminary desulfurization degree reaches more than 30%, addition product dibenzothiophene sulphone is obtained while desulfurization, improve its loading capacity to fuel oil medium sulphide content, desulfuration efficiency is high, easy to operate, safety, pollution-free.
The technical scheme that the present invention takes is:
A kind of gasoline high-efficiency environment friendly sulfur method, is characterized in that, specifically comprise the steps:
(1) preliminary desulfurization: get FeCl3 and KH2PO4 solution mixing and stirring according to mol ratio 1:4-5, the ionic liquid of 3-5% configuration is added in gasoline sample, control temperature of reaction is 32-35 DEG C, stirring reaction 15-25min, realizes removing of part sulphur in gasoline;
(2) oxidation sweetening: pass in autoclave by above-mentioned reaction solution, with the air in nitrogen replacement still 2-3 time, is then filled with the oxygen of certain pressure, being heated to temperature is 140-145 DEG C, in reaction solution, add the dibenzothiophene of 3-5%, open magnetic agitation, reaction 6-8h;
(3) collecting by filtration crystal: above-mentioned liquid is carried out filtration under diminished pressure and obtains dibenzothiophene sulphone crystal, filtrate is for subsequent use;
(4) preparing active carbon adsorption plate: configuration pH value is the sodium hydroxide solution of 7-7.5, is joined by gac in alkali lye, passes into ozone gas while stirring, carry out surface carry out oxidation 30-40min to gac, takes out, rinses post-drying with water, cooling;
(5) product is reclaimed: by filtrate obtained for step (3) according to certain flow, be sprayed onto on above-mentioned obtained charcoal absorption plate, it is 310-320 DEG C that the adsorption desulfurize couplings obtained is controlled Heating temperature, carries out underpressure distillation, reclaims sweet gasoline.
Further, in described step (2), the pressure-controlling of oxygen pressure is 0.8 ~ 1.0MPa.
Further, in described step (4), the volumetric molar concentration of sodium hydroxide solution is 6mol/L.
Further, in described step (5), the flow of liquid is 20-30mL/min.
Beneficial effect of the present invention is:
1, the present invention adopts ionic liquid to do preliminary desulfurization process to gasoline solution, and ionic liquid has large carrying capacity and dissolving power, plays modification, and reaction conditions is gentle, and preliminary desulfurization degree reaches more than 30%.
2, the oxidizing reaction of dibenzothiophene and sulfide is without the need to using catalyzer, with the oxygen of cheapness for oxygenant, the oxidation products obtained is separated automatically with gasoline, obtains addition product dibenzothiophene sulphone while desulfurization, efficiently make full use of raw material, environment protecting is remarkable.
3, the material cost of charcoal absorption plate is cheap, and raw material is easy to get, and adds activated carbon surface acidic-group by process, improve its loading capacity to fuel oil medium sulphide content, desulfuration efficiency is high, easy to operate, safety, pollution-free, absorption system can reuse.
Embodiment
Embodiment 1
A kind of gasoline high-efficiency environment friendly sulfur method, is characterized in that, specifically comprise the steps:
(1) preliminary desulfurization: get FeCl3 and KH2PO4 solution mixing and stirring according to mol ratio 1:4, add the ionic liquid of 3% configuration in gasoline sample, controlling temperature of reaction is 32 DEG C, stirring reaction 25min, realizes removing of part sulphur in gasoline;
(2) oxidation sweetening: above-mentioned reaction solution is passed in autoclave, with the air in nitrogen replacement still 3 times, be then filled with the oxygen of 0.8MPa, being heated to temperature is 140 DEG C, adds the dibenzothiophene of 3% in reaction solution, opens magnetic agitation, reaction 8h;
(3) collecting by filtration crystal: above-mentioned liquid is carried out filtration under diminished pressure and obtains dibenzothiophene sulphone crystal, filtrate is for subsequent use;
(4) preparing active carbon adsorption plate: configuration pH value is 7 and volumetric molar concentration is the sodium hydroxide solution of 6mol/L, is joined by gac in alkali lye, passes into ozone gas while stirring, surface is carried out to gac and carries out oxidation 30min, take out, rinse post-drying with water, cooling;
(5) product is reclaimed: by filtrate obtained for step (3) according to the flow of 20mL/min, be sprayed onto on above-mentioned obtained charcoal absorption plate, it is 310 DEG C that the adsorption desulfurize couplings obtained is controlled Heating temperature, carries out underpressure distillation, reclaims sweet gasoline.
It is 97.1% that Microcoulomb instrument measures desulfurization degree, and dibenzothiophene sulphone yield is 96.4%.
Embodiment 2
A kind of gasoline high-efficiency environment friendly sulfur method, is characterized in that, specifically comprise the steps:
(1) preliminary desulfurization: get FeCl3 and KH2PO4 solution mixing and stirring according to mol ratio 1:5, add the ionic liquid of 4% configuration in gasoline sample, controlling temperature of reaction is 33 DEG C, stirring reaction 20min, realizes removing of part sulphur in gasoline;
(2) oxidation sweetening: above-mentioned reaction solution is passed in autoclave, with the air in nitrogen replacement still 3 times, be then filled with the oxygen of 0.9MPa, being heated to temperature is 143 DEG C, adds the dibenzothiophene of 4% in reaction solution, opens magnetic agitation, reaction 7h;
(3) collecting by filtration crystal: above-mentioned liquid is carried out filtration under diminished pressure and obtains dibenzothiophene sulphone crystal, filtrate is for subsequent use;
(4) preparing active carbon adsorption plate: configuration pH value is 7.5 and volumetric molar concentration is the sodium hydroxide solution of 6mol/L, is joined by gac in alkali lye, passes into ozone gas while stirring, surface is carried out to gac and carries out oxidation 35min, take out, rinse post-drying with water, cooling;
(5) product is reclaimed: by filtrate obtained for step (3) according to the flow of 25mL/min, be sprayed onto on above-mentioned obtained charcoal absorption plate, it is 315 DEG C that the adsorption desulfurize couplings obtained is controlled Heating temperature, carries out underpressure distillation, reclaims sweet gasoline.
It is 97.0% that Microcoulomb instrument measures desulfurization degree, and dibenzothiophene sulphone yield is 96.1%.
Embodiment 3
A kind of gasoline high-efficiency environment friendly sulfur method, is characterized in that, specifically comprise the steps:
(1) preliminary desulfurization: get FeCl3 and KH2PO4 solution mixing and stirring according to mol ratio 1:5, add the ionic liquid of 5% configuration in gasoline sample, controlling temperature of reaction is 35 DEG C, stirring reaction 15min, realizes removing of part sulphur in gasoline;
(2) oxidation sweetening: above-mentioned reaction solution is passed in autoclave, with the air in nitrogen replacement still 3 times, be then filled with the oxygen of 1.0MPa, being heated to temperature is 145 DEG C, adds the dibenzothiophene of 5% in reaction solution, opens magnetic agitation, reaction 6h;
(3) collecting by filtration crystal: above-mentioned liquid is carried out filtration under diminished pressure and obtains dibenzothiophene sulphone crystal, filtrate is for subsequent use;
(4) preparing active carbon adsorption plate: configuration pH value is 7 and volumetric molar concentration is the sodium hydroxide solution of 6mol/L, is joined by gac in alkali lye, passes into ozone gas while stirring, surface is carried out to gac and carries out oxidation 40min, take out, rinse post-drying with water, cooling;
(5) product is reclaimed: by filtrate obtained for step (3) according to the flow of 30mL/min, be sprayed onto on above-mentioned obtained charcoal absorption plate, it is 320 DEG C that the adsorption desulfurize couplings obtained is controlled Heating temperature, carries out underpressure distillation, reclaims sweet gasoline.
It is 97.4% that Microcoulomb instrument measures desulfurization degree, and dibenzothiophene sulphone yield is 96.4%.
Claims (4)
1. a gasoline high-efficiency environment friendly sulfur method, is characterized in that, specifically comprises the steps:
(1) preliminary desulfurization: get FeCl3 and KH2PO4 solution mixing and stirring according to mol ratio 1:4-5, the ionic liquid of 3-5% configuration is added in gasoline sample, control temperature of reaction is 32-35 DEG C, stirring reaction 15-25min, realizes removing of part sulphur in gasoline;
(2) oxidation sweetening: pass in autoclave by above-mentioned reaction solution, with the air in nitrogen replacement still 2-3 time, is then filled with the oxygen of certain pressure, being heated to temperature is 140-145 DEG C, in reaction solution, add the dibenzothiophene of 3-5%, open magnetic agitation, reaction 6-8h;
(3) collecting by filtration crystal: above-mentioned liquid is carried out filtration under diminished pressure and obtains dibenzothiophene sulphone crystal, filtrate is for subsequent use;
(4) preparing active carbon adsorption plate: configuration pH value is the sodium hydroxide solution of 7-7.5, is joined by gac in alkali lye, passes into ozone gas while stirring, carry out surface carry out oxidation 30-40min to gac, takes out, rinses post-drying with water, cooling;
(5) product is reclaimed: by filtrate obtained for step (3) according to certain flow, be sprayed onto on above-mentioned obtained charcoal absorption plate, it is 310-320 DEG C that the adsorption desulfurize couplings obtained is controlled Heating temperature, carries out underpressure distillation, reclaims sweet gasoline.
2. a kind of gasoline high-efficiency environment friendly sulfur method according to claim 1, is characterized in that, in described step (2), the pressure-controlling of oxygen pressure is 0.8 ~ 1.0MPa.
3. a kind of gasoline high-efficiency environment friendly sulfur method according to claim 1, is characterized in that, in described step (3), the volumetric molar concentration of sodium hydroxide solution is 6mol/L.
4. a kind of gasoline high-efficiency environment friendly sulfur method according to claim 1, is characterized in that, in described step (5), the flow of liquid is 20-30mL/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192658A (en) * | 2017-12-20 | 2018-06-22 | 湖南大学 | The method of dibenzothiophenes in a kind of catalysis oxidation-filtering removal oil product |
| CN111961001A (en) * | 2020-08-14 | 2020-11-20 | 郑州大学 | Desulfurizing agent for removing dibenzothiophene and 4, 6-dimethyldibenzothiophene in oil product and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192658A (en) * | 2017-12-20 | 2018-06-22 | 湖南大学 | The method of dibenzothiophenes in a kind of catalysis oxidation-filtering removal oil product |
| CN111961001A (en) * | 2020-08-14 | 2020-11-20 | 郑州大学 | Desulfurizing agent for removing dibenzothiophene and 4, 6-dimethyldibenzothiophene in oil product and preparation method and application thereof |
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