CN101007963A - Method for removing sulfur-containing compound from carbon fuel by catalytic oxidation - Google Patents

Method for removing sulfur-containing compound from carbon fuel by catalytic oxidation Download PDF

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CN101007963A
CN101007963A CN 200710036632 CN200710036632A CN101007963A CN 101007963 A CN101007963 A CN 101007963A CN 200710036632 CN200710036632 CN 200710036632 CN 200710036632 A CN200710036632 A CN 200710036632A CN 101007963 A CN101007963 A CN 101007963A
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hydrocarbon fuel
sulfocompound
catalytic
sulphur
desulfurization
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CN100523134C (en
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路勇
王亚
高立达
毛继平
薛青松
刘晔
何鸣元
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East China Normal University
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Abstract

The invention relates to a catalytic oxidation method for removing sulfur-containing compound from hydrocarbon fuel, belonging to petroleum chemical industry field. The method takes air as oxidant, continuously oxidates the sulfur compound in hydrocarbon fuel in catalytic reactor at 150- 350 Deg. C and normal pressure into sulfoxide Sox, and the percentage of desulfurization reaches above 90%. The invention is characterized in that the post treatment for extraction of desulfurized hydrocarbon fuel is not complicated, and the process can be carried out continuously, it takes air as oxidant, which reduces cost, and it overcomes problems of high cost of hydrodesulphurization, loe efficiency of adsorption desulphurization, wastewater treatment and separation.

Description

The method of sulfocompound in a kind of catalytic oxidative desulfurization hydrocarbon fuel
Technical field
The present invention relates to the method for sulfocompound in a kind of catalytic oxidative desulfurization hydrocarbon fuel, belong to petrochemical industry.
Technical background
The environmental requirement of increasingly stringent makes world's oil refining industry face the severe challenge of producing low sulfur content cleaning hydrocarbon fuel.According to the plan of EPA, required in 2006 content of sulfur in gasoline less than 30 μ g/g, diesel oil sulphur content less than 15 μ g/g; European Union and Japan's plan are carried out stricter restriction to sulphur content.Tackle new environmental requirement, world major oil companies and scientific research personnel all be devoted to economy, efficiently in the hydrocarbon fuel sulfide remove Research on New and exploitation.Wherein, new technologies such as selective hydrogenation processing new catalyst and technology, petrol and diesel oil adsorption desulfurize, diesel bio desulfurization, selective catalytic oxidation desulfurization are particularly noticeable.
At present, sophisticated hydrogenating desulfurization technology is extensively to adopt both at home and abroad.It is good to use this method oil quality, the product yield height, but reaction conditions is very harsh, needs to adopt very high pressure, improves temperature of reaction simultaneously, has increased the difficulty of deep desulfuration, and the hydrogenation unit investment is big, and the process cost height causes the diesel oil cost significantly to rise.For the hydrogenating desulfurization of gasoline, the problem that the hydrogenation that must consider unsaturated hydrocarbons causes gasoline octane rating to reduce.According to estimation, reach the requirement for restriction of EPA to the diesel oil sulphur content, the expense of each refinery's technological transformation of employing hydrogenating desulfurization technology will be up to nearly 100,000,000 dollars; The economic evaluation of EPA shows that the cost of every hectolitre diesel oil will increase about 9 dollars.Therefore, the exploitation of non-hydrogenating desulfurization technology is subjected to more attention gradually, and has obtained very big development.
People have given to show great attention to adsorption desulfurize.The Idemitsu Kosen Co., Ltd. of Japan is respectively at the U.S. [US2005271913] and China [CN1678390, CN1671825] patent of having applied for fuel cell hydrogen feedstock adsorption desulfurize, patented invention a kind ofly contain sorbent material cerium oxide or metallic nickel, can under normal temperature, normal pressure, the mercaptan in propane, gasoline, kerosene, the gas oil, thioether, thiophene sulfides be removed to below the 0.1-0.2 μ g/g, effect not deviate from the absorption of benzothiophene kind sulfuration thing in the diesel oil but mention; U.S. Exxon company has announced a patent [US2005258077] that is used for the gasoline absorbing desulfurization of fuel cell hydrogen manufacturing, the sorbent material that this patent proposes is that nickel is distributed on silicon oxide and the alumina mixture carrier, under 230 ℃, can make the sulphur content in the gasoline be reduced to 0.5 μ g/g from 22 μ g/g; U.S. UTC Fuel Cells, LLC has applied for two gasoline, Ultra-deep Desulfurization of Diesel Fuels patented technology [CN1449592 in China, CN1413243A], patent has prepared a kind of nickel desulfurization reagent, in 150 ℃~235 ℃ scopes, gasoline, sulfide in diesel oil can be dropped to 0.05 μ g/g, but add about 10% in must liquid fuel within when oxycompound (methyl tertiary butyl ether, ethanol etc.) is arranged, sweetening agent is just effective, and it is effective to deviating from mercaptan, thioether, thiophene that patent is only mentioned sweetening agent, do not mention the validity to disubstituted dibenzothiophene.The S-Zorb chemisorption desulfurization technology of Phillips oil company [2000 NPRA Annual Meeting.AM-00-12] is that first cover is used for the industrialization technology of gasoline absorbing desulfurization in the world, again this technology was used for diesel fuel desulfurization afterwards, under the condition of 343~413 ℃ of temperature of reaction, pressure 0.7~2.1MPa, sulphur content in the gasoline is reduced to below the 25 μ g/g from 800 μ g/g, and the sulphur content in the diesel oil is reduced to below the 5 μ g/g from 434 μ g/g.U.S. Exxon company has also developed a kind of diesel deep desulfurization technology [US5454933], this technology is at first carried out hydrofining to diesel oil under than the demulcent condition, remove dibenzothiophene and substituting group derivatives class sulfide with absorption method again, the regeneration of sorbent material useable solvents adopts this technology that the diesel oil of sulfur-bearing 1000 μ g/g is reduced to below the sulphur content 10 μ g/g.Although absorption method has good sweetening effectiveness, have that the sorbent material consumption is big, regeneration is difficult, operate a series of problems such as discontinuous, expense height, so this method is also premature as a kind of efficient, economic hydrocarbon fuel desulfurization technology.The economic evaluation of EPA think existing adsorption desulfurize technology economically also can't with the hydrogenating desulfurization technology competition.
In view of the foregoing, the catalytic oxidation desulfurization technology has caused the attention of oil refining circle and academia.US20020035306 has reported acetic acid aqueous solution catalysis hydrogen peroxide oxidation-abstraction desulfurization system.They think that acetate and hydrogen peroxide effect generate Peracetic Acid, can remove the stable sulfide that is difficult to by hydrogenation and removing effectively.Oxidizing reaction is being lower than 100 ℃, and under the non-pressurized reaction conditions, dibenzothiophene sulfide and homologue thereof are adopted to have polar solvent extract by the selectivity oxidation then.This method can be reduced to 70 μ g/g by 4720 μ g/g with sulphur content in the diesel oil.Document [Energy﹠amp; Fuels.14 (2000) 1232] reported employing formic acid catalyzer, the research of the various sulfide of catalysis hydrogen peroxide oxidation can be with thioether, mercaptan, thionaphthene, dibenzothiophene and 4, oxidations such as 6-dimethyl Dibenzothiophene are removed.But because the cloud density on the sulphur atom is low in thiophene and the alkyl-substituted derivatives, can not be by hydrogen peroxide oxidation under mild conditions.Chinese patent CN01136396.7 discloses the method that ultrasonic-catalytic-oxidation desulfurization is produced ultra-low-sulphur diesel.They utilize TOAB (four octyl group amine bromides) is consisting of phase-transferring agent, and PTA (phospho-wolframic acid) is a catalyzer, H 2O 2Be oxygenant, under ultrasound condition, reacted 7 minutes,, the sulphur content in the diesel oil can be reduced to 19 μ g/g from 1867 μ g/g again by steps such as thermal treatment, solvent extractions.Chinese patent CN1554730A discloses a kind of method of catalyzed oxidation deep removal sulfide in petrol.It is catalyzer that this method adopts solid molecular sieves, hydrogen peroxide is an oxygenant, under 40 ℃-80 ℃ of temperature, normal pressure, can be with the main sulfide oxidation in the gasoline, oxidation products is that solvent extraction removes with methyl alcohol, acetonitrile, the trimethyl carbinol, water or its mixture, through separating the sulphur compound that can remove the 80-90% in the gasoline, the sulphur content in the FCC gasoline can be reduced to 18 μ g/g by 136 μ g/g.Reported a kind of method of utilizing HTS (Ti-MWW) catalytic oxidative desulfurization light-end products sulfide in the document [catalysis journal, 27 (7) 2,006 547], under 70 ℃, condition of normal pressure, acetonitrile: simulation oil product=1: 1 (10mL: 10mL), H 2O 2: S=4: 1, catalyzer: simulation oil product=1: 10, reacted 3 hours, the sulphur content in the light-end products can be reduced to below the 50 μ g/g by 1000 μ g/g.
As fully visible, in the disclosed various oxidation style, mainly adopt H both at home and abroad 2O 2As oxygenant, deviate from oxidation state sulfide (as sulfone or sulfoxide) with extraction agent at last.Although its oxidation effectiveness is better, desulfurization degree is higher, H 2O 2High Deng the oxygenant price, large usage quantity, follow-up extracting and separating be difficulty comparatively, and the extraction agent consumption is big, and expense is very high.In fact, the oxidation [Catalysis Today, 117 (2006) 199-205] of a large amount of alkene (one of chief component of gasoline) that exist can cause H in the true fuel oil 2O 2Oxygenant consumes fast, may cause the oxidation of the sulfide of trace existence to be difficult to take place; In addition, the existence of the impurity such as organic compounds containing nitrogen of trace also may cause the poisoning of catalyst system in the true fuel oil.Therefore, economic, the research and development of catalytic sweetening method is efficiently also shouldered heavy responsibilities.
Summary of the invention
The object of the present invention is to provide the selectivity catalytic air oxygen oxidizing method for removing of sulfide in a kind of hydrocarbon fuel.
The selectivity catalytic air oxygen oxidizing method for removing of sulfide in the hydrocarbon fuel provided by the invention is to be oxygenant with the air, utilizes fixed bed catalytic reactor that the sulfide in the hydrocarbon fuel is oxidized to oxysulfide (SOx) continuously, has high desulfurization rate.
The selectivity catalytic air oxygen oxidizing method for removing of sulfide carries out under normal pressure in the hydrocarbon fuel provided by the invention, and range of reaction temperature is optimized range of reaction temperature at 200 ℃~300 ℃ at 150 ℃~350 ℃.
The selectivity catalytic air oxygen oxidizing method for removing of sulfide in the hydrocarbon fuel provided by the invention, hydrocarbon fuel weight hourly space velocity scope is at 5~80h -1, optimize the weight hourly space velocity scope at 10-50h -1, optimization weight hourly space velocity scope is at 15~40h -1
The selectivity catalytic air oxygen oxidizing method for removing of sulfide in the hydrocarbon fuel provided by the invention, oxygen/sulphur (O 2/ S) span of control of mol ratio is 5~200.
Reaction evaluating carries out on the micro fixed-bed reactor of laboratory, catalyst levels 1.5 grams.For pure hydrocarbon reaction, simulate Sweet natural gas, liquefied petroleum gas (LPG) and liquid hydrocarbon fuel respectively with methane, propane and octane-iso, with methyl mercaptan, butyl thioether, thiophene, thionaphthene, 4, the 6-dimethyl Dibenzothiophene is simulated the sulfocompound in the hydrocarbon fuel respectively.The decreasing ratio of sulfocompound adopts the n-dodecane marker method by being furnished with the HP6850 type chromatographic determination of FID (hydrogen flame detector), with 30 meters HP-1 capillary columns in the octane-iso simulation oil product; The decreasing ratio of the sulfocompound in methane and propane mimic Sweet natural gas and the liquefied petroleum gas (LPG) adopts propane and methane marker method respectively, by being furnished with the HP6850 type chromatographic determination of FID (hydrogen flame detector), with 30 meters HP-1 capillary columns; The residual volume of sulphur also adopts microcoulomb sulphur detector (WK-2D type, Jiangsu Electrical Analysis Instrument Factory) to analyze to check and approve the stratographic analysis result in the partial reaction product.In the reaction end gas evaluation of sulfurous gas adopt the CP-3800 type chromatogram of being furnished with PFPD (pulsed flame photometric detector) of U.S. Varian and HP6890 5973N type chromatograph mass spectrometer identify.Show O in the reaction process with the HP6850 type stratographic analysis of being furnished with AT-plot 3000 type capillary chromatographic columns and TCD (thermal conductivity cell detector) 2Transform and only have the CO generation of tracer level fully.O 2Selectivity definition be: S O2=[oxygen that the oxidation organic sulfide consumes/total oxygen-consumption] * 100%; As, a part thionaphthene complete oxidation need consume 10.5 molecular oxygen [C 8H 6S (thionaphthene)+10.5O 2→ 8CO 2+ 3H 2O+SO 2]; If reaction system O 2/ S ratio is 30, O when then thionaphthene transforms fully 2Selectivity: (10.5/30) * 100%=35%.For true oil product, sulfur removal rate adopts microcoulomb sulphur detector (WK-2D type, Jiangsu Electrical Analysis Instrument Factory) to measure.
The selectivity catalytic air oxygen oxidizing method for removing of sulfide compared with prior art has following remarkable advantage in the hydrocarbon fuel provided by the invention:
(1) the sulfur-bearing hydrocarbon fuel does not need follow-up extraction after catalytic air oxygen oxidation sweetening is handled, and can realize the continuity operation of sulfur removal technology.
(2) use air oxidant, cost is low, and consumption is little, and sweetening effectiveness is obvious, has overcome hydrogenating desulfurization cost height in the past, and adsorption desulfurize efficient is low, the oxygenant of non-air oxidation sweetening, wastewater treatment and problem such as separate.
This method is oxygenant with the air, under 150 ℃-350 ℃, condition of normal pressure, utilizes catalyticreactor that the sulfide in the hydrocarbon fuel is oxidized to oxysulfide products such as (SOx) continuously, and desulfurization degree can reach more than 90%.The invention has the advantages that the high sulfur content oil product does not need complicated follow-up extraction after catalytic oxidation desulfurization is handled, and can realize the continuity operation of sulfur removal technology.The present invention's air oxidant, cost is low, and consumption is little, and sweetening effectiveness is obvious, has overcome hydrogenating desulfurization cost height in the past, and adsorption desulfurize efficient is low, the oxygenant of non-air oxidation sweetening, wastewater treatment and problem such as separate.
Description of drawings
Fig. 1 is 1.5wt%Pd/CeO 2O under the different material air speed on the catalyzer 2/ S compares the relation with desulfurization degree.
Fig. 2 is 1.5wt%Pt/CeO 2On the catalyzer under the differential responses temperature desulfurization degree with the relation in reaction times.
Embodiment
To specifically describe the present invention below in conjunction with embodiment, all embodiment all operate by the operational condition of technique scheme.In the specific embodiment, the catalyzer of employing is selected from CeO 2The Cu of load, Pd, Pt or CuZnAl composite oxides, but be not qualification to this patent.
Embodiment 1-3
With 1.5wt%Pd/CeO 2Be catalyzer [synthetic seeing for details: Applied Catalysis B, 53 (2004) 77-85], the octane-iso of sulfur-bearing 1000 μ g/g (thionaphthene is the sulphur source) is a raw material, is respectively 3.21,15.29 and 17.41h at 300 ℃, normal pressure, stock oil weight hourly space velocity -1Under the condition, investigated O 2The influence of/S ratio the results are shown in Figure 1.From Fig. 1 result as can be seen, reach the best O of maximum desulfurization degree on this catalyzer 2/ S ratio is about 30; 3.21,15.29 and 17.41h -1Weight hourly space velocity under, desulfurization degree is respectively>99%, 98% and 95%.Identify that through PFPD chromatogram and chromatograph mass spectrometer the sulfurous gas of reaction end gas is SO 2O 2Selectivity more than 30%.
1.5wt%Pt/CeO 2Also obtain the result identical on the catalyzer with embodiment 1-3.
Embodiment 4-6
1.5wt%Pt/CeO 2Be catalyzer [synthetic seeing for details: Journal of Catalysis, 229 (2005) 499-512] that the octane-iso of sulfur-bearing 1000 μ g/g (thionaphthene is the sulphur source) is a raw material, at normal pressure, O 2/ S than 30, stock oil weight hourly space velocity 15.29h -1Under the condition, investigated under 150,200,250,300 ℃, the thionaphthene decreasing ratio the results are shown in Figure 2 over time.From Fig. 2 result as can be seen, on this catalyzer best temperature of reaction at~300 ℃; Under the lower temperature of reaction, catalyzer can rapid deactivation.
Embodiment 7-8
5wt%Cu/CeO 2Be catalyzer [synthetic seeing for details: Applied Catalysis B, 28 (2000) 113-125] that the octane-iso of sulfur-bearing 1000 μ g/g (thionaphthene is the sulphur source) is a raw material, at normal pressure, O 2/ S than 17, stock oil weight hourly space velocity 40h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur reach>99%, O 2Selectivity be 61.7%; The decreasing ratio of sulphur reaches 97% in the time of 280 ℃, O 2Selectivity be 59.9%.At normal pressure, O 2/ S than 17, stock oil weight hourly space velocity 80h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur reach~70%.
Embodiment 9-11
With CuZnAl (Cu/Zn/Al mass ratio: 36/13/28) composite oxides [synthetic see for details " catalysis journal ", 27 (10) (2006) 857-862] be catalyzer, the octane-iso of sulfur-bearing 1000 μ g/g (thionaphthene is the sulphur source) is a raw material, at normal pressure, stock oil weight hourly space velocity 18h -1Under the condition, reach the O of decreasing ratio>99% of sulphur in the time of 300 ℃ 2/ S ratio is 90, O 2Selectivity be 11.7%; Reach the O of decreasing ratio>99% of sulphur in the time of 275 ℃ 2/ S ratio is 170, O 2Selectivity be 6.2%; 250 ℃, O 2/ S ratio is 170 o'clock, the decreasing ratio of sulphur reaches>and 95%, O 2Selectivity be 5.9%.
Embodiment 12
With 1.5wt%Pt/CeO 2Be catalyzer, the octane-iso of sulfur-bearing 1000 μ g/g (thiophene is the sulphur source) is a raw material, at normal pressure, O 2/ S than 15, stock oil weight hourly space velocity 15h -1Under the condition, the decreasing ratio of sulphur reaches 93% in the time of 300 ℃, O 2Selectivity be 37.2%; The decreasing ratio of sulphur reaches 91% in the time of 280 ℃, O 2Selectivity be 36.4%.
Embodiment 13
With 1.5wt%Pt/CeO 2Be catalyzer, the octane-iso of sulfur-bearing 1000 μ g/g (the butyl thioether is the sulphur source) is a raw material, at normal pressure, O 2/ S than 30, stock oil weight hourly space velocity 15h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur reach>99%, O 2Selectivity be 60%.
Embodiment 14
With 1.5wt%Pt/CeO 2Be catalyzer, the octane-iso of sulfur-bearing 500 μ g/g (4, the 6-dimethyl Dibenzothiophene is the sulphur source) is a raw material, at normal pressure, O 2/ S than 30, stock oil weight hourly space velocity 15h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur reach>99%, O 2Selectivity be 56.7%.
Embodiment 15-16
With 1.5wt%Pd/CeO 2Be catalyzer, methane (simulation Sweet natural gas) and the propane (simulated solution liquefied oil gas) of sulfur-bearing 300 μ g/g (methyl mercaptan) are raw material, at normal pressure, O 2/ S than 6, raw material weight hourly space velocity 15h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur all reach>99%, O 2Selectivity be 50%.Because Sweet natural gas and liquefied petroleum gas (LPG) are gas at normal temperatures and pressures, the SOx that sulfocompound wherein generates through catalyzed oxidation needs with sorbent material it to be removed from streams.
Embodiment 17
(the Cu/Zn/Al mass ratio: 36/13/28) composite oxides (synthetic " the catalysis journal ", 27 (10) (2006) 857-862 of seeing for details) are catalyzer, and the catalytically cracked gasoline of sulfur-bearing 407 μ g/g is a raw material, at normal pressure, O with CuZnAl 2/ S than 200, stock oil weight hourly space velocity 6h -1Under the condition, in the time of 300 ℃ the decreasing ratio of sulphur reach~75%, react and do not reduce in 50 hours.During rising temperature of reaction to 350 ℃, sulfur removal rate still remains on~and 75%.
Embodiment 18
With 1.5wt%Pd/CeO 2Be catalyzer, liquefied petroleum gas (LPG) is raw material (sulfur-bearing 200ppm), at normal pressure, O 2/ S than 30, raw material weight hourly space velocity 10h -1Under the condition, the decreasing ratio of sulphur>99% in the time of 300 ℃.

Claims (6)

1. the method for sulfocompound in the catalytic oxidative desulfurization hydrocarbon fuel, it is characterized in that with the air being oxygenant, utilize fixed bed catalytic reactor that the sulfide in the hydrocarbon fuel is oxidized to oxysulfide continuously, range of reaction temperature is at 150 ℃~350 ℃, and hydrocarbon fuel weight hourly space velocity scope is at 5~80h -1, oxygen/sulphur molar ratio range is 5~200.
2. the method for sulfocompound is characterized in that catalyst system therefor is selected from Pt/CeO in the fixed bed catalytic reactor in the catalytic oxidative desulfurization hydrocarbon fuel as claimed in claim 1 2, Pd/CeO 2, Cu/CeO 2Perhaps any one in the CuZnAl composite oxides.
3. the method for sulfocompound in the catalytic oxidative desulfurization hydrocarbon fuel as claimed in claim 1 is characterized in that temperature of reaction is 200 ℃~300 ℃.
4. the method for sulfocompound in the catalytic oxidative desulfurization hydrocarbon fuel as claimed in claim 1 is characterized in that the hydrocarbon fuel weight hourly space velocity is 10~50h -1
5. the method for sulfocompound in the catalytic oxidative desulfurization hydrocarbon fuel as claimed in claim 1 is characterized in that the hydrocarbon fuel weight hourly space velocity is 15~40h -1
6. the method for sulfocompound is characterized in that hydrocarbon fuel in the catalytic oxidative desulfurization hydrocarbon fuel as claimed in claim 1, is meant Sweet natural gas, liquefied petroleum gas (LPG), gasoline, kerosene or diesel oil.
CNB2007100366323A 2007-01-19 2007-01-19 Method for removing sulfur-containing compound from carbon fuel by catalytic oxidation Expired - Fee Related CN100523134C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192655A (en) * 2018-01-24 2018-06-22 中国石油大学(华东) A kind of method for extracting removing Sulfur Compounds from Crude Oils
CN108525658A (en) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening
CN108525660A (en) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization
CN114345329A (en) * 2021-11-08 2022-04-15 大连理工大学 Application of normal-pressure ultra-deep desulfurization catalyst

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US8906227B2 (en) * 2012-02-02 2014-12-09 Suadi Arabian Oil Company Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108525658A (en) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 The method of the catalyst system and sulfur-bearing hydrocarbon oxidation sweetening of sulfur-bearing hydrocarbon oxidation sweetening
CN108525660A (en) * 2017-03-03 2018-09-14 中国石油化工股份有限公司 A kind of method of sulfur-bearing hydrocarbon oxygenation desulfurization
CN108525660B (en) * 2017-03-03 2022-05-17 中国石油化工股份有限公司 Method for oxygen-adding and desulfurizing sulfur-containing hydrocarbon
CN108192655A (en) * 2018-01-24 2018-06-22 中国石油大学(华东) A kind of method for extracting removing Sulfur Compounds from Crude Oils
CN114345329A (en) * 2021-11-08 2022-04-15 大连理工大学 Application of normal-pressure ultra-deep desulfurization catalyst

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