CN100408658C - Method of diesel oil oxidation extraction and desulfurization - Google Patents
Method of diesel oil oxidation extraction and desulfurization Download PDFInfo
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- CN100408658C CN100408658C CNB2005100737714A CN200510073771A CN100408658C CN 100408658 C CN100408658 C CN 100408658C CN B2005100737714 A CNB2005100737714 A CN B2005100737714A CN 200510073771 A CN200510073771 A CN 200510073771A CN 100408658 C CN100408658 C CN 100408658C
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Abstract
The present invention relates to a method for oxidating, extracting and desulfurizing diesel oil, which comprises the following steps: a) hydrofined diesel oil or diesel oil not hydrofined and a phase transfer catalyst are mixed at a normal temperature at normal pressure and stirred until the catalyst is dissolved, hydrogen peroxide is added to react for 30 to 300 minutes, and organic sulfide existing in the diesel oil is converted into sulphone and/or sulphoxide to obtain oxidated diesel oil; b) the phase transfer catalyst is separated out after the temperature of the oxidated diesel oil in step a) is lowered to the room temperature; c) the oxidated diesel oil without the phase transfer catalyst separated out is treated with a reducing agent water solution with the concentration of 5 to 20% to remove unreacted hydrogen peroxide; d) the sulphone and/or the sulphoxide is removed from the oxidated diesel oil obtained in step c) with an extracting agent to obtain low sulfur diesel oil having a sulfur content lower than that 350 ppm.
Description
Technical field
The present invention relates to a kind of method of oxidation sweetening, relate to a kind of method of diesel oil oxidation extraction and desulfurization particularly.
Background technology
The SO that organic sulfide in the oil fuel produces after burning
XCan not only cause acid rain, can also make the three-way catalyst of automobile engine tail gas purification system produce irreversible poisoning, therefore cause that people pay close attention to widely.Making with extra care of distillate is requisite important process process in the petrochemical complex, exactly in order to remove organic sulfide and the organic nitrogen compound in the oil fuel, to satisfy the demand of environment protection.Traditional treating process is hydrofining, promptly by hydrogenation organic sulfide and organic nitrogen compound is converted into hydrogen sulfide and ammonia, thereby reaches the purpose that removes sulphur, nitrogen.Although traditional unifining process is effective, also have following problems: 1, investment is big; Except building the high temperature high pressure process device, also want organizational system hydrogen production device (if not reforming hydrogen), sulfur recovery facility etc.2, consume hydrogen owing to relate to High Temperature High Pressure in the course of processing, so tooling cost is higher; 3, owing in the course of processing, there is hypertoxic hydrogen sulfide to produce, unavoidably cause environmental pollution.4, hydrofining can remove the non-thiophene-type sulfide in the diesel oil effectively, but to thiophene-type sulfide particularly thionaphthene, dibenzothiophene and derivative thereof remove very difficulty.Remove this part sulfide, the essential transformation has hydro-refining unit now, improves service temperature and hydrogen dividing potential drop, and this must cause increasing investment cost, improves tooling cost, reduces catalyzer work-ing life and reduces oil quality.Along with the increasingly stringent of legislations of environmental protection, press for a kind of more economically, environmental friendliness and more effective low-sulfur diesel-oil (sulphur content＜350ppm sulphur) production method more.
United States Patent (USP) 6,160,193 disclose a kind of fractional oil desulfurizing method: " earlier selective oxidation becomes sulphur and nitrogen oxide to increase its polarity with nitrogenous compound with the sulfur-bearing in the distillate, again with one and distillate in the immiscible solvent extraction of hydro carbons these contain oxysulfide, contain oxynitride to reach the purpose of desulfurization removing nitric." strong oxidizer that uses of this patent is that strongly-acid oxygenant such as peroxyboric acid, persulfuric acid and temperature of reaction are higher, thereby must cause the generation of a large amount of side reactions with this method processing diesel oil, be unfavorable for the raising of diesel quality; The strongly-acid oxygenant has the very strong corrodibility of corrosion to equipment simultaneously, and is also unfriendly to environment.
United States Patent (USP) 6,274,785 pairs of above-mentioned patents have been done improvement, have changed highly acid strong oxidizer into peracetic acid.Since the peracetic acid oxidation capacity a little less than, thereby temperature of reaction is higher, side reaction is more, the amount of the hydrogen peroxide of producing peracetic acid simultaneously and being consumed is also bigger, is unfavorable for reducing running cost.
United States Patent (USP) 6,402,940 disclose a kind of fractional oil desulfurizing method: " with sulfurous fuels oil 50～130 ℃ with oxygenant/extraction agent (a small amount of hydrogen peroxide; a large amount of formic acid and be lower than the mixing solutions that 25% water is formed) after the mixing solutions reaction; after the fractionate aqueous solutions; remove a small amount of residue formic acid and water in deoiling by distillation, use the calcium oxide drying again, sulfone or and sulfoxide that the oil that obtains is fallen with the not extraction that removes in deoiling by an adsorption column that alumina adsorbant is housed." this sulfur removal technology is owing to use a large amount of formic acid, thereby unfriendly to environment; Simultaneously service temperature is higher, and side reaction is more, and this not only consumes a large amount of hydrogen peroxide, increases running cost, and is unfavorable for the raising (as colourity etc.) of oil quality.
What above-mentioned three patents adopted is water oil two-phase system, and speed of response is slower, normally adopts the raising temperature of reaction to improve speed of response.
Also have and adopt other method to improve speed of response, as United States Patent (USP) 6,402,939 and 6,500,219 disclose a kind of desulfurization of fuel oil method: " oil and alkyl peroxide (or hydrogen peroxide), tensio-active agent, metal catalyst (as tungstate etc.) are mixed; under 75 ℃ of temperature; the container that will fill this mixing solutions is inserted in the ultra-sonic generator; the organic sulfide in the oil is oxidized to sulfone or/and sulfoxide; again with polarity extracting agent with sulfone or/and sulfoxide from oil, extract, thereby reach the purpose of desulfurization." although this patent utilization ultrasonic wave, tensio-active agent and catalyzer accelerated speed of response; temperature of reaction still higher (＞70 ℃), this not only can't be avoided many side reactions, consumes a large amount of hydrogen peroxide; increase running cost, but also to diesel quality influential (as colourity etc.); Not mentioned tensio-active agent and the catalyzer of how reclaiming of this patent simultaneously.
United States Patent (USP) 5,958,224 also disclose a kind of with hydrotreatment and oxidation depth desulfurization combination process: " with oil fuel and a peroxide metal complex oxygenant effect of hydrotreatment; the organic sulfide in the oil fuel is oxidized to sulfone or/and sulfoxide, again by an adsorption column that sorbent material is housed with the sulfone in the oil or/and sulfoxide adsorbs removes." because the employed catalyzer of this method is one to be insoluble to the solid adsorbent of oil fuel, can only be dissolved in the chloro-hydrocarbons (as methylene dichloride), because it is chloro-hydrocarbons toxicity is big, unfriendly to environment.
Chinese patent (application number is 03107599.1) discloses a kind of method for pre-hydrofined oil ultra-deep desulfurization, be with hydrofining diesel oil with consist of Q
3[XM
12O
40] phase-transfer catalyst and after the mixture formed of aqueous hydrogen peroxide solution fully stirs, under gentle relatively reaction conditions (temperature of reaction≤60 ℃, normal pressure), the organic sulfide that will be present in the diesel oil is converted into sulfone or/and sulfoxide promptly obtains oxidated diesel oil.The oxidated diesel oil that will obtain after will handling again is by a polar solvent, optionally remove wherein most of sulfone or and sulfoxide, to remove at last most of sulfone or and the diesel oil of sulfoxide by an adsorption column that sorbent material is housed, to obtain a sulphur content be 0ppm or be lower than 10ppm.(the pre-hydrogenated diesel oil of sulphur content≤1000ppm) but is difficult to remove in a large number for the pre-hydrogenated diesel oil of high density and the sulphur in the not hydrorefined diesel oil, therefore has great defective, remains further raising because this catalyzer can only be handled lower concentration.
Summary of the invention
The object of the present invention is to provide a kind of method of diesel oil oxidation extraction and desulfurization.
Both can remove sulfide such as dibenzothiophene and the derivative thereof that the extremely difficulty in the hydrofining diesel oil removes effectively by method provided by the invention, also can remove sulfide such as thionaphthene and derivative thereof that general oxidation sweetening is difficult to remove effectively, used catalyzer not only has extremely strong catalytic activity and selectivity to organic sulfide, and with diesel oil (reactant) directly as solvent, water is unique product of hydrogen peroxide, thereby this technological process is friendly more to environment.
For achieving the above object, the method for diesel oil oxidation extraction and desulfurization provided by the invention, key step comprises:
A) under the normal temperature and pressure, hydrofining diesel oil or not hydrorefined diesel oil are mixed with phase-transfer catalyst, wherein the content of phase-transfer catalyst is relevant with the content of sulfide in the diesel oil, phase-transfer catalyst: sulfide=1: 15-20 (mol ratio), be stirred to catalyst dissolution, add the metering ratio or be in excess in the hydrogen peroxide that measures ratio slightly, reacted 30-300 minute, the organic sulfide that will be present in the diesel oil is converted into sulfone or/and sulfoxide promptly obtains oxidated diesel oil;
B) after the oxidated diesel oil of step a is reduced to room temperature, isolate phase-transfer catalyst;
C) be that the reductive agent aqueous solution of 5-20% is handled the oxidated diesel oil isolated phase-transfer catalyst with concentration, remove unreacted hydrogen peroxide, wherein the reductive agent aqueous solution: oxidated diesel oil=1: 5-20 (volume ratio);
D) oxidated diesel oil that step c is obtained is removed sulfone with extraction agent or/and sulfoxide, wherein extraction agent: oxidated diesel oil=1: 1 (volume ratio);
The expression formula of described phase-transfer catalyst is Q
3[XM
nO
q], in the formula:
1≤n≤11；
Q is a quaternary ammonium salt cationic, consists of (C
xH
2x+1)
4N
+, x 〉=8, described quaternary ammonium salt cationic is one of following quaternary ammonium salt cationic:
(C
8H
17)
4N
+、(C
12H
25)
4N
+、(C
16H
33)
4N
+、(π-C
5H
5N+C
16H
33)、[(C
18H
37)(75％)+(C
16H
33)(25％)]
2N
+(CH
3)
2、(C
18H
37)
2N
+(CH
3)
2。
Preferred quaternary ammonium salt cationic is one of following quaternary ammonium salt cationic:
(C
12H
25)
4N
+、(C
16H
33)
4N
+、(π-C
5H
5N
+C
16H
33)、
[(C
18H
37)(75％)+(C
16H
33)(25％)]N
+(CH
3)
3、(C
18H
37)N
+(CH
3)
3。
Best quaternary ammonium salt cationic is one of following quaternary ammonium salt cationic:
(C
16H
33)
4N
+、(π-C
5H
5N
+C
16H
33)、
[(C
18H
37)(75％)+(C
16H
33)(25％)]N
+(CH
3)
3、(C
18H
37)N
+(CH
3)
3。
X is phosphorus, silicon or arsenic, and preferred phosphorus or arsenic are preferably phosphorus.
M is molybdenum or tungsten, preferably tungsten.
The described reductive agent aqueous solution is the aqueous solution of solubility hydrosulphite, solubility sulphite or solubility thiosulphate; Preferred reductive agent is solubility hydrosulphite or solubility sulphite; Best reductive agent is the solubility thiosulphate.
Described extraction agent is methyl alcohol, formic acid, ethanol, acetate, dimethyl sulfoxide (DMSO) (DMSO), two formyl ammoniums (DMF), acetonitrile (CH
3CN) or/and N-N-methyl-2-2-pyrrolidone N-(NMP), preferred N-Methyl pyrrolidone (NMP), N, N-dimethyl formyl ammonium (DMF) is or/and acetonitrile.
Described hydrofining diesel oil is meant that sulphur content is the refined diesel oil of 100ppm to 2000ppm, and preferred sulphur content is lower than the refined diesel oil of 500ppm; The diesel oil of hydrogenation is not meant that sulphur content is straight-run diesel oil or the FCC diesel oil of 500ppm to 8000ppm.
Separation method in the step (b) refers to and filters or/and centrifugation preferred centrifugation.
Compare with known technology, the present invention has the following advantages:
1, to sulfide particularly in the diesel oil difficult thionaphthene that removes and derivative thereof and dibenzothiophene and derivative thereof have the selective oxidation ability, can realize the normal temperature and pressure oxidation, running cost can reduce greatly.
2, the recyclable utilization of catalyzer has not only reduced production cost, but also has prevented because of influencing oil quality in the catalyst residue oil.
3, the sulphur content in the hydrofining diesel oil can be reduced to low-sulfur level (sulphur content＜350ppm).
Embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1: Preparation of catalysts
The expression formula of phase-transfer catalyst of the present invention is Q
3[XM
nO
q], in the formula: 1≤n≤11;
Q is quaternary ammonium salt cationic (C
xH
2x+1)
4N
+), the carbon chain lengths that has a group in this quaternary ammonium salt cationic at least is more than or equal to 8 carbon atoms.Be understood that thus the quaternary ammonium salt ion in the phase-transfer catalyst of the present invention one of can be following:
(C
8H
17)
4N
+、(C
12H
25)
4N
+、(C
16H
33)
4N
+、(π-C
5H
5N
+C
16H
33)、[(C
18H
37)(75％)+(C
16H
33)(25％)]
2N
+(CH
3)
2、(C
18H
37)
2N
+(CH
3)
2。
X is phosphorus, silicon or arsenic, and effect is preferably selected phosphorus or arsenic for use, and what effect was best is phosphorus.
M is molybdenum or tungsten, and what effect was best is tungsten.
Need explanatorily be, as long as Q, X, M meet above-mentioned condition, those skilled in the art all can prepare phase-transfer catalyst according to following method, therefore lift catalyzer [(C
18H
37) N
+(CH
3)
3] [PW
3O
q] be illustrative examples, preparation as follows:
Take by weighing the 1.87g wolframic acid and be suspended in the 10.0ml hydrogen peroxide, 60 ℃ of oil bath vigorous stirring 30min, room temperature is reduced in dissolving; Take by weighing SODIUM PHOSPHATE, MONOBASIC 0.39g, be dissolved in 5ml water, stir 5min under the room temperature, it is joined in the hydrogen peroxide solution of wolframic acid, stir, regulate pH=2-3; Get quaternary ammonium ammonia salt octadecyl trimethyl ammonium chloride 2.6g again and be dissolved in the 10ml dehydrated alcohol, splash in the above-mentioned mixing solutions, vigorous stirring generates white precipitate immediately simultaneously, and the dropping time is 1-2h, continues to stir 3-4h; At last after filtration, get deionised water, vacuum-drying gets the white solid catalyzer.Be called catalyst A.
Embodiment 2
(1) get the 25ml sulphur content be the hydrofining diesel oil of 340ppm in a triangular flask, at room temperature add 0.02248g catalyst A (grinding the back), add hydrogen peroxide 0.11ml again, vigorous stirring 30min, (2) reclaim catalyzer with above-mentioned processing diesel oil centrifugation.(3) add in the diesel oil of hypo solution after above-mentioned steps (2) is handled of 13ml 5%, stir 30min after, remove lower aqueous solution with separating funnel after, wash three times (25ml at every turn) after, use the 10g anhydrous sodium sulfate drying.(4) ([N-Methyl pyrrolidone: (N-Methyl pyrrolidone+water)]=75-95%) extraction separates lower floor's composite extractant, the re-extract secondary with the 25ml composite extractant with dry diesel oil.The diesel oil that obtains is measured sulphur content with microcoulometry, and the results are shown in Table 1.
Embodiment 3
The temperature of step 1 is 30 ℃, and all the other operational conditions are with embodiment 2.
Embodiment 4
Extraction agent N-N-methyl-2-2-pyrrolidone N-(NMP), all the other operational conditions are with embodiment 2.
Embodiment 5
(1) get the 25ml sulphur content be the not hydrogenation FCC diesel oil of 2150ppm in a triangular flask, in 30 ℃ of oil baths, add 0.1124g catalyst A (grinding the back), add hydrogen peroxide 1ml again, vigorous stirring 3h, (2) reclaim catalyzer with above-mentioned processing diesel oil centrifugation.(3) add in the diesel oil of hypo solution after above-mentioned steps (2) is handled of 20ml 20%, stir 30min after, remove lower aqueous solution with separating funnel after, wash three times (25ml at every turn) after, use the 10g anhydrous sodium sulfate drying.(4) ([N-methyl pyrrole-2-pyrrolidone: (N-N-methyl-2-2-pyrrolidone N-+water)]=75-95%) separates lower floor's composite extractant, re-extract three times with the extraction of 25ml composite extractant with dry diesel oil.The diesel oil that obtains is measured sulphur content with microcoulometry, and the results are shown in Table 1.
Embodiment 6
Extraction agent is the N-N-methyl-2-2-pyrrolidone N-, and all the other operational conditions are with embodiment 5.
Embodiment 7
(1) get the 25ml sulphur content be the exquisite diesel oil of hydrogenation of 1700ppm in a triangular flask, room temperature adds 0.1147g catalyst A (grinding the back), adds hydrogen peroxide 0.316ml again, vigorous stirring 30min, (2) reclaim catalyzer with above-mentioned processing diesel oil centrifugation.(3) add in the diesel oil of hypo solution after above-mentioned steps (2) is handled of 20ml10%, stir 30min after, remove lower aqueous solution with separating funnel after, wash three times (25ml at every turn) after, use the 10g anhydrous sodium sulfate drying.(4) with dry diesel oil 25ml acetonitrile: DMF=4: the composite extractant extraction of 1 (volume ratio), separate lower floor's composite extractant, the re-extract secondary.The diesel oil that obtains is measured sulphur content with microcoulometry, and the results are shown in Table 1.
Embodiment 8
Extraction agent N-N-methyl-2-2-pyrrolidone N-(NMP), all the other operational conditions are with embodiment 7.
Embodiment 9
Extraction agent dimethyl sulfoxide (DMSO) (DMSO), all the other operational conditions are with embodiment 7.
Embodiment 10
Phosphorus tungsten ratio is 1: 4, is called catalyst B, and all the other operation stepss are with embodiment 1.
Embodiment 11
(1) get the 25ml sulphur content be the not hydrogenation FCC diesel oil of 340ppm in a triangular flask, in 30 ℃ of oil baths, add 0.1g catalyst B (grinding the back), add hydrogen peroxide 0.15ml again, vigorous stirring 1h, (2) reclaim catalyzer with above-mentioned processing diesel oil centrifugation.(3) add in the diesel oil of hypo solution after above-mentioned steps (2) is handled of 10ml 10%, stir 30min after, remove lower aqueous solution with separating funnel after, wash three times (25ml at every turn) after, use the 10g anhydrous sodium sulfate drying.(4) (the composite extractant extraction of [N-Methyl pyrrolidone: (N-Methyl pyrrolidone+water)]=75-95%) separates lower floor's composite extractant, the re-extract secondary with 25ml with dry diesel oil.The diesel oil that obtains is measured sulphur content with microcoulometry, and the results are shown in Table 1.
Embodiment 12
Phosphorus tungsten ratio is 1: 1, is called catalyzer C, and all the other operational conditions are with embodiment 1.
Embodiment 13
Phosphorus tungsten ratio is 1: 2, is called catalyzer D, and all the other operational conditions are with embodiment 1.
Embodiment 14
Phosphorus tungsten ratio is 1: 5, is called catalyzer E, and all the other operational conditions are with embodiment 1.
Embodiment 15
Phosphorus tungsten ratio is 1: 6, is called catalyzer F, and all the other operational conditions are with embodiment 1.
Embodiment 16
Phosphorus tungsten ratio is 1: 10, is called catalyzer G, and all the other operational conditions are with embodiment 1.
Embodiment 17
Phosphorus tungsten ratio is 1: 11, is called catalyzer H, and all the other operational conditions are with embodiment 1.
Embodiment 18
Select catalyzer C for use, all the other operational conditions are with embodiment 11.
Embodiment 19
Select catalyzer D for use, all the other operational conditions are with embodiment 11.
Embodiment 20
Select catalyzer E for use, all the other operational conditions are with embodiment 11.
Embodiment 21
Select catalyzer F for use, all the other operational conditions are with embodiment 11.
Embodiment 22
Select catalyzer G for use, all the other operational conditions are with embodiment 11.
Embodiment 23
Select catalyzer H for use, all the other operational conditions are with embodiment 11.
Table 1. test-results
The diesel oil sulphur content of producing by the present invention all is lower than 350ppm, under the prerequisite that guarantees productive rate (composite extractant that uses the present invention to propose), reach the clean diesel III of European countries (standard of sulphur content＜350ppm), have in addition reached the clean diesel IV of the European countries (standard of sulphur content＜50ppm).Illustrate that the present invention has good sweetening power.
Claims (2)
1. the method for a diesel oil oxidation extraction and desulfurization, key step comprises:
A) under the normal temperature and pressure, hydrofining diesel oil or not hydrorefined diesel oil are mixed with phase-transfer catalyst, phase-transfer catalyst wherein: the mol ratio of sulfide=1: 15-20, be stirred to catalyst dissolution, add the metering ratio or be in excess in the hydrogen peroxide that measures ratio, reacted 30-300 minute, the organic sulfide that will be present in the diesel oil is converted into sulfone or/and sulfoxide promptly obtains oxidated diesel oil;
B) after the oxidated diesel oil of step a is reduced to room temperature, isolate phase-transfer catalyst;
C) be that the reductive agent aqueous solution of 5-20% is handled the oxidated diesel oil isolated phase-transfer catalyst with concentration, remove unreacted hydrogen peroxide, wherein the reductive agent aqueous solution: the volume ratio of oxidated diesel oil=1: 5-20;
D) oxidated diesel oil that step c is obtained is removed sulfone with extraction agent or/and sulfoxide, wherein extraction agent: the volume ratio of oxidated diesel oil=1: 1;
The expression formula of described phase-transfer catalyst is Q
3[XM
nO
q], in the formula:
Q is a quaternary ammonium salt cationic; X is phosphorus, silicon or arsenic; M is molybdenum or tungsten; 1≤n≤11;
Described quaternary ammonium salt cationic is one of following quaternary ammonium salt cationic:
(C
8H
17)
4N
+、(C
12H
25)
4N
+、(C
16H
33)
4N
+、(π-C
5H
5N
+C
16H
33)、[(C
18H
37)(75％)+(C
16H
33)(25％)]
2N
+(CH
3)
2、(C
18H
37)
2N
+(CH
3)
2、(C
18H
37)N
+(CH
3)
3；
The described reductive agent aqueous solution is that solubility hydrosulphite, solubility sulphite are or/and the aqueous solution of solubility thiosulphate;
Described extraction agent is that methyl alcohol, formic acid, ethanol, acetate, dimethyl sulfoxide (DMSO), two formyl ammoniums, acetonitrile are or/and the N-N-methyl-2-2-pyrrolidone N-.
2. the method for claim 1 is characterized in that, described hydrofining diesel oil is meant that sulphur content is the refined diesel oil of 100ppm to 2000ppm, and the diesel oil of hydrogenation is not meant that sulphur content is straight-run diesel oil or the FCC diesel oil of 500ppm to 8000ppm.
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|---|---|---|---|
| CNB2005100737714A CN100408658C (en) | 2005-05-24 | 2005-05-24 | Method of diesel oil oxidation extraction and desulfurization |
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| CN100408658C true CN100408658C (en) | 2008-08-06 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101921613A (en) * | 2009-06-17 | 2010-12-22 | 中国科学院大连化学物理研究所 | Method for preparing ultra low sulfur diesel |
| US8926825B2 (en) * | 2010-03-19 | 2015-01-06 | Mark Cullen | Process for removing sulfur from hydrocarbon streams using hydrotreatment, fractionation and oxidation |
| CN102492457A (en) * | 2011-12-14 | 2012-06-13 | 南京大学 | Microwave-driven diesel oil oxidation desulfurizing 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 |
| CN109207195B (en) * | 2018-10-18 | 2021-04-23 | 佛山市光烨环保科技有限公司 | Light circulating oil ultrasonic catalytic oxidation extraction desulfurization process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003044129A1 (en) * | 2001-11-20 | 2003-05-30 | Consejo Superior De Investigaciones Cientificas | Method of oxidising sulphur compounds present in gasoline, kerosene and diesel fractions |
| CN1534082A (en) * | 2003-03-28 | 2004-10-06 | 中国科学院大连化学物理研究所 | Preparation method of super low sulfur diesel oil |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003044129A1 (en) * | 2001-11-20 | 2003-05-30 | Consejo Superior De Investigaciones Cientificas | Method of oxidising sulphur compounds present in gasoline, kerosene and diesel fractions |
| CN1534082A (en) * | 2003-03-28 | 2004-10-06 | 中国科学院大连化学物理研究所 | Preparation method of super low sulfur diesel oil |
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