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EP1175471B1 - Verfahren zur erzeugung von erdölprodukten mit niedrigem schwefelgehalt durch entschwefelung von extrakten - Google Patents

Verfahren zur erzeugung von erdölprodukten mit niedrigem schwefelgehalt durch entschwefelung von extrakten Download PDF

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Publication number
EP1175471B1
EP1175471B1 EP00925374A EP00925374A EP1175471B1 EP 1175471 B1 EP1175471 B1 EP 1175471B1 EP 00925374 A EP00925374 A EP 00925374A EP 00925374 A EP00925374 A EP 00925374A EP 1175471 B1 EP1175471 B1 EP 1175471B1
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compounds
solvent
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process according
type
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French (fr)
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EP1175471A1 (de
Inventor
Pedro Da Silva
Rapha[L Le Gall
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TotalEnergies Marketing Services SA
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TotalFinaElf France SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step

Definitions

  • the invention relates to a process for obtaining petroleum products. which could possibly be used, either for the formulation of fuel for compression-ignition internal combustion engine (of the type diesel), either as fuel, as well as petroleum product of the type diesel and the by-products obtained by this process.
  • Diesel oils which are currently on the market in France in the form of fuels for diesel engines, are refinery products that contain sulfur in quantity at more than 0.05% by weight (500 ppm, or parts per million); however, increasingly stringent sulfur content standards are envisaged, in particular by the European Union, for the year 2000 ( ⁇ 350 ppm) and for 2005 ( ⁇ 50 ppm).
  • the catalytic hydrodesulfurization process consumes large quantities of hydrogen and requires operating at increasingly high temperatures and pressures or at a speed hourly space of the lower charge, and with more catalysts when you want to eliminate these ultimate amounts of sulfur contained in these organosulfur compounds; this makes them increasingly expensive installations and the less attractive process on the economic plan.
  • microorganisms as biocatalysts specific, genetically modified, we can stop the reaction to stage of intermediate products such as hydroxyphenyl-benzenesulfinates or their derivatives, which are soluble in water and can therefore be extracted from hydrocarbon feedstocks.
  • intermediate products such as hydroxyphenyl-benzenesulfinates or their derivatives, which are soluble in water and can therefore be extracted from hydrocarbon feedstocks.
  • the implementation of such a process requires the formation of an emulsion oil / water and biocatalyst, in a reactor with a volume ratio can be 25/75%, and causes the drawback of using processing capacities with high volumes.
  • US Patent 5,232,854 describes an advanced desulfurization process a hydrocarbon feed, comprising a hydrodesulfurization step conventional followed by a biocatalytic desulfurization step by incubation of the charge in the presence of oxygen with microorganisms such as those described in the patents cited above, and a step of separation of the hydrocarbon effluent having a sulfur content ⁇ 500 ppm, residues in the form of non-organic sulphides.
  • a method does not make it possible to reduce the sulfur content of feedstock treated at rates well below 500 ppm, for example around 50 ppm.
  • the aim of the present invention is therefore to improve advanced desulphurization of hydrocarbon feedstocks with a high content of sulfur, without implementing temperature and high pressure, and while promoting the by-products obtained.
  • the Applicant has established that it was particularly judicious to couple stages of extraction and oxidative desulfurization, which take place under conditions of low temperature and pressure, close to room temperature and atmospheric pressure, and without hydrogen consumption, therefore very interesting economically, and in particular concentrate the most refractory organosulfur compounds by a extraction process, then treating the extracts obtained by a process desulfurization by oxidation, so as to separate the effluents hydrocarbons obtained with low sulfur content of the compounds oxidized organosulfur and to recover these by-products; these latter can then be valued, after treatment, in particular as detergents.
  • the invention relates to a process for obtaining petroleum products of the improved quality diesel type, from a diesel cutter containing organosulfur compounds of the type dibenzothiophenes and / or their derivatives, initial boiling points and final generally between about 170 and 480 ° C, characterized in what it involves at least two stages, one, a), of extraction liquid / liquid in which the diesel cut is brought into contact with a solvent, so as to obtain a low-grade diesel-type raffinate in sulfur and aromatic compounds and an extract rich in solvent and high content of sulfur and aromatic compounds, and the other, b), oxidation of the sulfur compounds of the extract, so as to obtain, after separation, a heavy diesel fuel effluent of low to low sulfur content, and a residue comprising organosulfur compounds oxidized.
  • the two steps are performed at pressures less than or equal to 1 MPa, and at temperatures between room temperature and 100 ° C.
  • the solvent used in step a) is chosen from the group consisting of methanol, acetonitrile, monomethylformamide, dimethyl formamide, dimethylacetamide, N-methylpyrolidone, dimethylsulfoxide and furfural.
  • step b) consists into a bio-desulfurization in which it is treated in a reactor the extract, optionally freed from the solvent, preferably at pressure atmospheric, in the presence of a biocatalyst in the aqueous phase, comprising an appropriate strain of microorganisms generating enzymes capable of oxidizing organosulfur compounds.
  • step b) when this is a bio-desulfurization, is followed by a first step c) of separation of the oily phase containing the hydrocarbon effluent and the aqueous phase, the latter containing the biocatalyst and the residue consisting of compounds of the type organosulfinates, in particular benzenesulfinates and / or their derivatives; these are formed by the opening of thiophenic cycles by oxidation.
  • the separation of the residue and the biocatalyst is performed in a second separation step d), which consists of either extraction with a polar solvent or on exchange resins ions, either by filtration or by adsorption on a support solid polar.
  • step b) consists of a chemical oxidation; this can be carried out in particular with oxidizing agents of the peroxide type.
  • the residue from step b), obtained after separation is consisting of compounds of the sulfoxide or sulfone type.
  • the biosulfurization step is carried out at pressures below 1 MPa and in particular at atmospheric pressure, in the presence of air, and at temperatures between the temperature ambient and 40 ° C.
  • the starting diesel cut is a cut of direct distillation, or comes from a hydrocracking operation, catalytic cracking, visbreaking or coking, it has a sulfur content generally greater than or equal to 1% by weight.
  • the hydrocarbon effluent from step b) has a point final boiling point less than or equal to 380 ° C.
  • the method according to the invention comprises a additional stage of distillation or decantation of the extract of step a) making it possible to obtain a top product rich in solvent, which is recovered and recycled in the extraction stage, and a tail product depleted in solvent which is introduced in step b); he can also be envisaged a stage of distillation of the raffinate from stage a), in order to recover the small amount of solvent it still contains.
  • the method further comprises an additional hydrotreatment step of the hydrocarbon effluent obtained in step c), in particular of hydrodesulfurization in mild conditions.
  • Benzenesulfinate type compounds obtained by the process according to the invention after having been subjected to a treatment additional such as oxidation followed by alkylation or alkylation, can be used as hydrotropic agents or surfactants, especially in the manufacture of detergents.
  • step b) The chemical oxidation of step b) can be carried out in phase homogeneous at low temperature (around 70-80 ° C) and at pressure atmospheric, in the presence of a peroxidizing agent (for example hydrogen peroxide) and an acid catalyst such as acetic acid or sulfuric acid.
  • a peroxidizing agent for example hydrogen peroxide
  • an acid catalyst such as acetic acid or sulfuric acid.
  • the separation of the sulfones obtained and the effluent hydrocarbon can be done on an adsorbent mass, as by example of silica gel. Any other type of oxidation can be used, and in particular oxidation by oxone (peroxy-monosulfate of potassium) is also possible.
  • a first advantage presented by the method according to the invention is allow the use of hydrocarbon cuts, for example of the type diesel fuel, with an initial boiling point of around 170 ° C and a point final boiling point of about 375 ° C (the boiling point temperatures indicated are measured according to the TBP distillation method "True boiling point "), having already undergone conventional catalytic hydrodesulfurization and with a residual sulfur content of less than 500 ppm, and concentrate, thanks to the liquid-liquid type extraction step with a solvent with increased selectivity for dibenzothiophenes and their derivatives, these compounds in the extract phase which is sent to step next.
  • the raffinate obtained in this extraction consists of a hydrocarbon feedstock with a low content of sulfur-containing compounds and aromatics, which is sent to the engine diesel pool (the pool is the designation designating all the basic products used for make a petroleum product).
  • a second advantage is to carry out the two pressure stages less than 1 MPa and at a temperature less than 100 ° C, and preferably at atmospheric pressure and at room temperature.
  • LCO type cuts Light cycle oil very aromatic cut from effluents from a catalytic cracking unit
  • the liquid-liquid extraction step is carried out in a conventional manner, with against the current, in an extraction column comprising as packing for example of fixed discs and rings, discs rotary or static mixers, preferably having 5 to 10 theoretical stages, at a temperature between 30 ° C and 100 ° C, and under a pressure between 0.1 and 1 MPa; the volume report solvent to the charge is generally from 0.2 / 1 to 5/1.
  • the solvent is preferably chosen from the group of solvents allowing to extract at least part of the mono and polyaromatic compounds and sulfur, this group consisting of methanol, acetonitrile, monomethylformamide, dimethyl formamide, dimethylacetamide, N-methylpyrolidone, dimethylsulfoxide and furfural. It is also possible to add to the solvent a cosolvent which can be a linear or branched alcohol.
  • Step b) of oxidation of the sulfur-containing compounds is carried out so as to obtaining, after separation, a hydrocarbon effluent of the heavy diesel type with reduced sulfur content, which can be sent to the fuel pool domestic, and a residue comprising organosulfur compounds oxidized.
  • a diesel-type raffinate is obtained, having a sulfur content of 0.8% by weight, which after having been freed from the solvent by distillation, is sent via line 4 to a hydrodesulfurization reactor 5, operating under usual conditions.
  • a partial pressure of hydrogen of 2.5 MPa a temperature of 340 ° C, an hourly space velocity (VVH) of 1.1 h -1 , a ratio of the flow of hydrogen to the load of 125 Nl / l (Nl being "Normal" liters), in the presence of a cobalt-molybdenum catalyst supported on alumina, so as to obtain an effluent having a sulfur content of 29 ppm and a density of 0.825, sent via line 20 the engine diesel pool and which meets the specifications planned for 2005; an extract having a sulfur content of 5% by weight is recovered via line 6, which, after having been freed in a distillation column 7, of the solvent which is recycled by line 8 to the extraction column 2, is sent via line 9 to the bio-desulfurization reactor
  • reaction products from line 12 are introduced into a separator 13 from which is recovered by line 14 a hydrocarbon effluent of the heavy diesel type, containing 1% by weight of sulfur, which to be sent to the pool domestic fuel oil (sulfur content ⁇ 0.2%), must undergo hydrodesulfurization under conditions similar to those prevailing in reactor 5 (for example at a temperature between 330 and 340 ° C.) so as to obtain a content of 0, 17% by weight of sulfur.
  • the hydrocarbon cut used comes from a light Arabic diesel of direct distillation, has an initial distillation point of 180 ° C and an end distillation point 380 ° C, and underwent a hydrodesulfurization treatment so as to have a sulfur content of 200 ppm; this cut undergoes a fractionation to obtain a head product which is a cut whose point final boiling point is below 328 ° C and has a sulfur content of 40 ppm, therefore meets the specification for diesel in 2005 engine, and a tail product whose initial boiling point is higher than 328 ° C (cut 328-380 ° C), containing sulfur compounds refractories in high concentration and having a sulfur content of 720 ppm, which is sent to the next extraction step.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (11)

  1. Verfahren zum Erhalten von Kraftstoff-Erdölprodukten mit verbesserter Qualität aus einem Kraftstoff-Zuschnitt, das Organoschwefel-Verbindungen vom Typ der Dibenzothiophene und/oder deren Derivate enthält, mit Anfangs- und End-Siedepunkten im Bereich zwischen ungefähr 170 und 480°C, dadurch gekennzeichnet, dass es aus mindestens zwei Schritten besteht mit:
    einem Schritt (a) einer Flüssig/Flüssig-Extraktion, bei der der Kraftstoff-Zuschnitt mit einem Lösungsmittel in Kontakt gebracht wird, um ein Kraftstoffraffinat mit niedrigem Gehalt an Schwefel- und aromatischen Verbindungen und einen Extrakt, der reich an Lösungsmitteln ist und einen hohen Gehalt an Schwefel- und aromatischen Verbindungen aufweist, zu erhalten, und
    einem anderen Schritt (b) einer Oxidation der Schwefelverbindungen des Extrakts, um nach einer Trennung einen Schwerkraftstoff-Kohlenwasserstoffabfluss mit niedrigem Schwefelgehalt und einen Rest, der oxidierte Organoschwefelverbindungen umfasst, zu erhalten.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die zwei Schritte bei Drücken von weniger oder gleich 1 MPa und bei Temperaturen im Bereich zwischen Umgebungstemperatur und 100°C durchgeführt werden.
  3. Verfahren gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das für den Schritt (a) verwendete Lösungsmittel aus der Gruppe ausgewählt wird, die aus Methanol, Acetonitril, Monomethylformamid, Dimethylformamid, Dimethylacetamid, N-Methylpyrrolidon, Dimethylsulfoxid und Furfural besteht.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Schritt (b) aus einer Bioentschwefelung besteht, bei der eine Behandlung in einem Extraktionsreaktor, gegebenenfalls von Lösungsmittel befreit, vorzugsweise bei Atmosphärendruck, in Gegenwart eines Biokatalysators in wässriger Phase stattfindet, welcher einen geeigneten Mikroorganismus-Stamm umfasst, der Enzyme erzeugt, die zum Oxidieren der Organoschwefelverbindungen in der Lage sind.
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Schritt (b) gefolgt wird von einem ersten Schritt (c) der Trennung der Ölphase, die den Kohlenwasserstoffabfluss und die wässrige Phase enthält, wobei das letztere den Biokatalysator und einen Rest enthält, der sich aus Organosulfinat-Verbindungen, insbesondere aus Benzolsulfinaten und/oder deren Derivaten, zusammensetzt.
  6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass die Trennung des Rests und des Biokatalysators durchgeführt wird in einem zweiten Trennschritt (d), der aus einer Extraktion mittels eines polaren Lösungsmittels oder über Ionenaustauscherharzen, oder einer Filtration, oder einer Adsorption an einem polaren festen Träger besteht.
  7. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Schritt (b) aus einer chemischen Oxidation besteht.
  8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass die Oxidation in Gegenwart von Peroxyd-Oxidationsmitteln durchgeführt wird.
  9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Anfangs-Kraftstoffzuschnitt aus einer Direktdestillation stammt oder von der Durchführung eines Hydrocrackens, eines katalytischen Crackens, einer Viskoreduktion oder einer Koksfaktion herrührt.
  10. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Anfangs-Kraftstoffzuschnitt einen Schwefelgehalt von mehr oder gleich 1 Gewichts-% aufweist.
  11. Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es einen zusätzlichen Schritt der Destillation oder Dekantierung des Extrakts des Schritts (a) umfasst, wodurch es gestattet wird, ein Kopfprodukt reich an Lösungsmitteln, welches zurückgewonnen und dem Extraktionsschritt wieder zugeführt wird, sowie ein an Lösungsmittel verarmtes Schwanzprodukt zu erhalten, welches dem Schritt (b) zugeführt wird.
EP00925374A 1999-05-05 2000-05-03 Verfahren zur erzeugung von erdölprodukten mit niedrigem schwefelgehalt durch entschwefelung von extrakten Expired - Lifetime EP1175471B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9905700 1999-05-05
FR9905700A FR2793256B1 (fr) 1999-05-05 1999-05-05 Procede d'obtention de produits petroliers a faible taux de soufre par desulfuration d'extraits
PCT/FR2000/001188 WO2000068342A1 (fr) 1999-05-05 2000-05-03 Procede d'obtention de produits petroliers a faible taux de soufre par desulfuration d'extraits

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EP1175471A1 EP1175471A1 (de) 2002-01-30
EP1175471B1 true EP1175471B1 (de) 2002-12-04

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US (1) US6638419B1 (de)
EP (1) EP1175471B1 (de)
AT (1) ATE229063T1 (de)
DE (1) DE60000934T2 (de)
ES (1) ES2187468T3 (de)
FR (1) FR2793256B1 (de)
PT (1) PT1175471E (de)
WO (1) WO2000068342A1 (de)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1993169A (zh) * 2004-08-02 2007-07-04 国际壳牌研究有限公司 从包含天然气或惰性气体的气流中脱除硫醇的方法
US8715489B2 (en) 2005-09-08 2014-05-06 Saudi Arabian Oil Company Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US7744749B2 (en) 2005-09-08 2010-06-29 Saudi Arabian Oil Company Diesel oil desulfurization by oxidation and extraction
WO2007049287A2 (en) * 2005-10-28 2007-05-03 Indian Oil Corporation Limited Method for bio-oxidative desulfurization of liquid hydrocarbon fuels and product thereof
US7906013B2 (en) 2006-12-29 2011-03-15 Uop Llc Hydrocarbon conversion process
US20080159928A1 (en) * 2006-12-29 2008-07-03 Peter Kokayeff Hydrocarbon Conversion Process
US7799208B2 (en) * 2007-10-15 2010-09-21 Uop Llc Hydrocracking process
US7803269B2 (en) 2007-10-15 2010-09-28 Uop Llc Hydroisomerization process
US7794585B2 (en) * 2007-10-15 2010-09-14 Uop Llc Hydrocarbon conversion process
US7794588B2 (en) * 2007-10-15 2010-09-14 Uop Llc Hydrocarbon conversion process to decrease polyaromatics
US7790020B2 (en) * 2007-10-15 2010-09-07 Uop Llc Hydrocarbon conversion process to improve cetane number
US9279087B2 (en) * 2008-06-30 2016-03-08 Uop Llc Multi-staged hydroprocessing process and system
US8008534B2 (en) * 2008-06-30 2011-08-30 Uop Llc Liquid phase hydroprocessing with temperature management
US8999141B2 (en) 2008-06-30 2015-04-07 Uop Llc Three-phase hydroprocessing without a recycle gas compressor
US8518241B2 (en) * 2009-06-30 2013-08-27 Uop Llc Method for multi-staged hydroprocessing
US8221706B2 (en) * 2009-06-30 2012-07-17 Uop Llc Apparatus for multi-staged hydroprocessing
WO2011002745A1 (en) * 2009-07-01 2011-01-06 Saudi Arabian Oil Company Membrane desulfurization of liquid hydrocarbons using an extractive liquid membrane contactor system and method
US8741127B2 (en) * 2010-12-14 2014-06-03 Saudi Arabian Oil Company Integrated desulfurization and denitrification process including mild hydrotreating and oxidation of aromatic-rich hydrotreated products
US8741128B2 (en) * 2010-12-15 2014-06-03 Saudi Arabian Oil Company Integrated desulfurization and denitrification process including mild hydrotreating of aromatic-lean fraction and oxidation of aromatic-rich fraction
RU2458104C1 (ru) * 2011-06-22 2012-08-10 Общество с ограниченной ответственностью "ЛУКОЙЛ-Нижегородский научно-исследовательский и проектный институт по переработке нефти" (ООО "ЛУКОЙЛ-Нижегородниинефтепроект") Способ получения дизельного топлива
US9005433B2 (en) * 2011-07-27 2015-04-14 Saudi Arabian Oil Company Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion
KR102001695B1 (ko) 2011-07-29 2019-10-04 사우디 아라비안 오일 컴퍼니 방향족 분리를 이용한 수소화처리 및 이성화 통합 공정
EP2737019A2 (de) * 2011-07-29 2014-06-04 Saudi Arabian Oil Company Wasserstoffbehandlung extrahierter aromatischer kohlenwasserstoffströme
EP2737022B1 (de) 2011-07-29 2017-10-04 Saudi Arabian Oil Company Selektives hydrierungsverfahren für mitteldestillate
KR101985559B1 (ko) 2011-09-27 2019-06-03 사우디 아라비안 오일 컴퍼니 산화적 탈황 반응 생성물의 선택적 액체-액체 추출
KR101489546B1 (ko) * 2011-10-24 2015-02-06 에스케이이노베이션 주식회사 중간 유분 내 방향족 저감 및 고품질 경유의 제조 방법
US20120138449A1 (en) * 2012-02-12 2012-06-07 King Abdulaziz City for Science and Technology (KACST) Method of removing sulfur from crude oil and diesel using ionizing radiation
US10450516B2 (en) 2016-03-08 2019-10-22 Auterra, Inc. Catalytic caustic desulfonylation
CN114621817A (zh) * 2020-12-08 2022-06-14 中石油克拉玛依石化有限责任公司 脱硫溶剂及脱硫方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002888A (en) * 1990-01-05 1991-03-26 Institute Of Gas Technology Mutant microorganisms useful for cleavage of organic C-S bonds
US5104801A (en) * 1990-01-05 1992-04-14 Institute Of Gas Technology Mutant microorganisms useful for cleavage of organic c-s bonds
US5132219A (en) * 1990-02-28 1992-07-21 Institute Of Gas Technology Enzymes from Rhodococcus rhodochrous strain ATCC No. 53968, Bacillus sphaericus strain ATCC No. 53969 and mixtures thereof for cleavage of organic C--S bonds of carbonaceous material
US5232854A (en) * 1991-03-15 1993-08-03 Energy Biosystems Corporation Multistage system for deep desulfurization of fossil fuels
IT1283233B1 (it) * 1996-03-12 1998-04-16 Eniricerche Spa Arthrobacter sp. e suo impiego per la desolforazione di combustibili fossili
US6402940B1 (en) * 2000-09-01 2002-06-11 Unipure Corporation Process for removing low amounts of organic sulfur from hydrocarbon fuels

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ES2187468T3 (es) 2003-06-16
EP1175471A1 (de) 2002-01-30
FR2793256B1 (fr) 2001-07-27
DE60000934D1 (de) 2003-01-16
PT1175471E (pt) 2003-03-31
ATE229063T1 (de) 2002-12-15
FR2793256A1 (fr) 2000-11-10
DE60000934T2 (de) 2003-05-08
US6638419B1 (en) 2003-10-28
WO2000068342A1 (fr) 2000-11-16

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