CN1315993C - Method for reducing sulfur content of fuel oil - Google Patents
Method for reducing sulfur content of fuel oil Download PDFInfo
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- CN1315993C CN1315993C CNB2005100178359A CN200510017835A CN1315993C CN 1315993 C CN1315993 C CN 1315993C CN B2005100178359 A CNB2005100178359 A CN B2005100178359A CN 200510017835 A CN200510017835 A CN 200510017835A CN 1315993 C CN1315993 C CN 1315993C
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Abstract
The present invention discloses a method for reducing sulfur contents in fuel oil, and 10 to 100 parts by weight of solid acidic organic matter come into contact with the mixtures of 50 to 300 parts by weight of fuel oil, 15 to 100 parts by weight of hydrogen peroxide and 1 part by weight of sulphuric acid. When reaction temperature is from 0 to 100 DEG C, and pressure is normal pressure, reaction is carried out for 1 to 60 minutes; then, generated sulfone and sulfoxide are removed through solvent extraction or adsorbent adsorption so as to obtain low-sulfur fuel oil. By using the method of the present invention, reaction time can be greatly shortened, and production cost is reduced.
Description
Technical field
The invention belongs to hydrocarbon oil refining process, particularly a kind of method that reduces the sulphur content in the oil fuel.
Background technology
At present, vehicle exhaust has become the main source of atmospheric pollution.Contained sulphur compound is a kind of objectionable impurities in the oil fuel, and the burning back generates SOx and causes forming acid rain.In addition, SOx has obvious facilitation to the discharging of HC, CO, NOx and particulate matter in the vehicle exhaust, and the noble metal catalyst in the vehicle exhaust convertor is poisoned; SOx also can corrode engine, reduces the life-span of engine.In view of the harm of the sulphur compound in the oil fuel, strict oil fuel sulfur-bearing standard has been issued in each major country of the world, area in succession.
In the face of the restriction of strict content of sulphur compounds and the market great demand to the low-sulfur clean fuel, countries in the world are devoted to develop various desulfurization of fuel oil technology one after another.Desulfurization of fuel oil technology commonly used at present is divided into hydrogenating desulfurization (HDS) and non-hydrogenating desulfurization (NHDS) two big classes.Hydrodesulfurization reaction condition harshness, plant investment is big, and the process cost height causes the oil fuel cost significantly to rise.Non-hydrogenating desulfurization mainly comprises oxidation sweetening and biological desulphurization, oxidation sweetening is divided into chemical catalytic oxidation method, photocatalytic oxidation and ultrasonic wave catalytic oxidation etc. again, wherein the research of chemical catalytic oxidation method is more, and oxygenant commonly used has hydrogen peroxide, peroxycarboxylic acid, ion exchange resin etc.United States Patent (USP) 20040007501 (application number) adopts Peracetic Acid and acetate to make oxygenant, after two hours the sulphur compound in the diesel oil is oxidized to sulfone or sulfoxide etc. in reaction about 60 ℃, adopts the absorption agent that contains zinc or nickel that sulfone or sulfoxide are separated again.United States Patent (USP) 6673236 adopts hydrogen peroxide, ethanol and metal oxide to make oxygenant, after one hour, the sulphur compound in the diesel oil is oxidized to sulfone or sulfoxide etc. 40～50 ℃ of reactions, adopts the methanol solvate extracting that sulfone is separated from diesel oil with sulfoxide again.The shortcoming of these oxygenants is that side reaction is more.United States Patent (USP) 20040154959 (application number) adopts the ion exchange resin that contains acidic-group of perfluor replacement or the acid organism that loads on the inoganic solids to make catalyzer, 25 ℃ the reaction 5 hours after, sulphur compound in the diesel oil is oxidized to sulfone or sulfoxide, can avoids the generation of side reaction.But the ion exchange resin cost that contains acidic-group that the used perfluor of this method replaces is higher, and the reaction times is oversize, is unfavorable for continuous large-scale industrialized.
Summary of the invention
The present invention be directed to that the prior art cost is higher, the reaction times is oversize, be unfavorable for shortcomings such as continuous large-scale industrialized and a kind of method that reduces the content of sulphur compounds in the oil fuel is provided, use that the investment of this method is little, process cost is low, can carry out the continuous large-scale suitability for industrialized production.
The inventive method is: solid acid organism and oil fuel, hydrogen peroxide contacts with sulfuric acid mixture, sulfuric acid wherein: hydrogen peroxide: oil fuel: the organic ratio of weight and number of solid acid is 1: 15～100: 50～300: 10～100, in temperature of reaction is 0～100 ℃, optimum temperature is 20～60 ℃, under condition of normal pressure, reacted 1～60 minute, the optimum reaction times is 1～20 minute, sulphur compound in the oil fuel is oxidized to sulfone and sulfoxide, remove sulfone and sulfoxide by solvent extraction or adsorbent method again, obtain low sulphur fuel oil, wherein said solid acid organism is to contain carboxylic acid group's acidic resins or contain sulfonic acidic resins, the acidic resins that contain the carboxylic acid group generally recommend to use polyacrylic resin, contain sulfonic acidic resins and generally recommend to use the polyoxyethylene alkylphenyl sulfonate resin.
The oil fuel of indication is the fraction of 60 ℃～350 ℃ of boiling ranges among the present invention, comprises gasoline and diesel oil distillate.
The extraction solvent that utilizes during solvent extraction among the present invention is an extraction solvent commonly used in this area, as N, and N～dimethyl formamide or dioxane etc., extracting process adopts conventional solvent extraction method.
The sorbent material that the present invention adopts is a conventional sorbent material in this area, and as silica gel, aluminum oxide, 13X molecular sieve or carclazyte etc., adsorption method adopts conventional method.
The used oxygenant of the inventive method is cheap, helps large-scale industrial production.
The present invention compares with United States Patent (USP) 20040154959 (application number), and temperature of reaction is high slightly or suitable, but the reaction times be reduced in 20 minutes from 5 hours, the reaction times shortens greatly; The used solid acid resin of the present invention is the ordinary resin on the market in addition, does not need further to be processed into the resin that perfluor replaces, so cost reduces greatly.These characteristics make the present invention more help large-scale industrial production, and can reduce production costs.
Embodiment 1:
Adding 100 gram concentration in the beaker of 1000ml respectively is that 40% hydrogen peroxide solution and 1 gram concentration are 98% the vitriol oil, stir, adding 100 gram particles more directly is the polyacrylic resin of 0.1～1.0mm, under 50 ℃ of condition of normal pressure, soak half an hour, be filled into the polyacrylic resin of above-mentioned immersion in the reactor and dry up the liquid that adheres on the resin with nitrogen, cyclohexane solution 60 grams that contain 2% dibenzothiophene are at normal temperatures by this pillar, 3 minutes duration of contact, the collection flowing liquid also evaporates hexanaphthene in water-bath, remaining solid is carried out Infrared spectroscopy, and the result shows that dibenzothiophene has been oxidized to corresponding sulfone.
Embodiment 2:
50 gram particles of packing in a φ 30mm glass column directly are the polyacrylic resin of 0.1～1.0mm, keep column temperature at 25 ℃, with concentration is that 98% the vitriol oil, 1 gram, concentration are that 30% hydrogen peroxide solution 140 grams and the mixture that contains cyclohexane solution 300 grams of 2% dibenzothiophene are squeezed into the polyacrylic resin post with pump from bottom to top, 20 minutes cycling time, flowing liquid is after oily water separation, organic phase is evaporated hexanaphthene, remaining solid is carried out Infrared spectroscopy, and the result shows: dibenzothiophene has been oxidized to corresponding sulfone.
Embodiment 3:
80 gram particles of packing in a φ 30mm glass column directly are the polyacrylic resin of 0.1～1.0mm.Keep column temperature at 40 ℃, with concentration is that 98% the vitriol oil, 1 gram, concentration are that the mixture of 50% hydrogen peroxide solution 80 grams and sulphur content straight-run diesel oil 250 grams that are 450ppm is from bottom to top by the polyacrylic resin post, reacted 10 minutes, flowing liquid is after minute oily water separation, get upper strata diesel oil and use N mutually, N～three times (agent-oil ratio 1: 1) of dimethyl formamide extraction analyzes the diesel oil after making with extra care, its sulphur content 80ppm.
Embodiment 4:
The particle diameter of packing in a φ 30mm glass column is polyacrylic resin 50 grams of 0.1～1.0mm, keep column temperature at 30 ℃, with concentration is that 98% the vitriol oil, 1 gram, concentration are that the mixture of 30% hydrogen peroxide solution 60 grams and sulphur content catalytic diesel oil 200 grams that are 5000ppm is from bottom to top by the polyacrylic resin post, reacted 15 minutes, flowing liquid is after minute oily water separation, get upper strata diesel oil and restrain 13X molecular sieve adsorption 1 hour with 50 mutually, analyze the diesel oil after making with extra care, its sulphur content 800ppm.
Embodiment 5:
The particle diameter of packing in a φ 30mm glass column is polystyrolsulfon acid type resin 100 grams of 0.1～1.0mm, keep column temperature at 60 ℃, with concentration is that 98% the vitriol oil, 1 gram, concentration are that the mixture of 50% hydrogen peroxide solution 200 grams and sulphur content gasoline 150 grams that are 350ppm is from bottom to top by polystyrolsulfon acid type resin column, reacted 10 minutes, flowing liquid is after minute oily water separation, get upper strata gasoline mutually with 50 gram carclazyte absorption 1 hour, analyze the gasoline after making with extra care, its sulphur content 40ppm.
Embodiment 6
With embodiment 5, just the sulphur content of gasoline is 1200ppm, and the reaction times is 15 minutes, analyzes the gasoline after making with extra care, its sulphur content 500ppm.
Embodiment 7:
With embodiment 5, the particle diameter of just packing in a φ 30mm glass column is polyacrylic resin 30 grams of 0.1～1.0mm, the gasoline after upper strata diesel oil is made with extra care with three (agent-oil ratio 1: 1) analyses of dioxane extraction, its sulphur content 80ppm.
Claims (4)
1, a kind of method that reduces sulphur content in the oil fuel, it is characterized in that: solid acid organism and oil fuel, hydrogen peroxide contacts with sulfuric acid mixture, sulfuric acid wherein: peroxidation oxygen: oil fuel: the organic ratio of weight and number of solid acid is 1: 15～100: 50～300: 10～100, in temperature of reaction is 0～100 ℃, pressure is to react under the condition of normal pressure 1～60 minute, remove the sulfone and the sulfoxide of generation again by solvent extraction or adsorbent method, obtain low sulphur fuel oil, wherein said solid acid organism is to contain carboxylic acid group's acidic resins or contain sulfonic acidic resins, and described oil fuel is the fraction of 60 ℃～350 ℃ of boiling ranges.
2, method according to claim 1 is characterized in that: temperature of reaction is 20～60 ℃, and the reaction times is 1～20 minute.
3, method according to claim 1 and 2 is characterized in that: the solid acid organism is a polyacrylic resin.
4, method according to claim 1 and 2 is characterized in that: the solid acid organism is the polyoxyethylene alkylphenyl sulfonate resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100178359A CN1315993C (en) | 2005-08-01 | 2005-08-01 | Method for reducing sulfur content of fuel oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100178359A CN1315993C (en) | 2005-08-01 | 2005-08-01 | Method for reducing sulfur content of fuel oil |
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| CN1730616A CN1730616A (en) | 2006-02-08 |
| CN1315993C true CN1315993C (en) | 2007-05-16 |
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| CNB2005100178359A Active CN1315993C (en) | 2005-08-01 | 2005-08-01 | Method for reducing sulfur content of fuel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110229693A (en) * | 2019-07-03 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of method that solid acid coupled ion liquid extracts oxidation sweetening to fuel oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6673236B2 (en) * | 2001-08-29 | 2004-01-06 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Method for the production of hydrocarbon fuels with ultra-low sulfur content |
| CN1624081A (en) * | 2004-10-24 | 2005-06-08 | 西南石油学院 | Process for catalyzing oxygenizing desulfurizing diesel oil |
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- 2005-08-01 CN CNB2005100178359A patent/CN1315993C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6673236B2 (en) * | 2001-08-29 | 2004-01-06 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Method for the production of hydrocarbon fuels with ultra-low sulfur content |
| CN1624081A (en) * | 2004-10-24 | 2005-06-08 | 西南石油学院 | Process for catalyzing oxygenizing desulfurizing diesel oil |
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Address after: 100029 Beijing City, Chaoyang District Hui Street No. 6 Co-patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Patentee after: China Petrochemical Group Corp. Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Co-patentee before: Luoyang Petrochemical Engineering Co., China Petrochemical Group Patentee before: China Petrochemical Group Corp. |
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