WO2017144460A1 - Procédé pour la désulfuration par oxydation de carburants liquides - Google Patents

Procédé pour la désulfuration par oxydation de carburants liquides Download PDF

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Publication number
WO2017144460A1
WO2017144460A1 PCT/EP2017/053927 EP2017053927W WO2017144460A1 WO 2017144460 A1 WO2017144460 A1 WO 2017144460A1 EP 2017053927 W EP2017053927 W EP 2017053927W WO 2017144460 A1 WO2017144460 A1 WO 2017144460A1
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Prior art keywords
phase
catalyst
organic sulfur
sulfur compounds
fuel
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PCT/EP2017/053927
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German (de)
English (en)
Inventor
Jakob Albert
Peter Wasserscheid
Benjamin BERTLEFF
Johannes CLAUSSNITZER
Wolfgang Korth
Andreas Jess
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Friedrich Alexander Universitaet Erlangen Nuernberg
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Friedrich Alexander Universitaet Erlangen Nuernberg
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Classifications

    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • hydrodesulfurization the hydrogenating conversion of the organic sulfur compounds contained in a fuel to heterogeneous catalysts such as cobalt-molybdenum or nickel-molybdenum fixed bed. Catalysts.
  • the fuel is preheated together with hydrogen-rich gas and reacts within a reactor under pressures of 20 bar to 170 bar at the solid catalyst located there. The hydrogenation reaction taking place on the catalyst ultimately leads to H 2 S and the hydrogenated hydrocarbon radical RH.
  • Hydrogenating desulfurization is particularly suitable for the desulfurization of diesel fuel and gasoline, but also for the desulfurization of vacuum gas oil.
  • the HDS process in deep desulphurisation reaches its value of 10 ppmw set by the stricter limits
  • a catalyst volume of up to 500 m 3 is needed to desulfurize 400 m 3 of fuel per hour.
  • typical overall pressures are 30 bar
  • the temperatures for the process are in a temperature range between 310 ° C to 370 ° C
  • for diesel fuel and kerosene are with 40 bar to 100 bar and temperatures between 330 ° C and 400 ° C sharper conditions necessary.
  • the desulphurisation of vacuum gas oils takes place at 170 bar and 425 ° C. Vacuum residue oils, on the other hand, can not be desulfurized at present.
  • An alternative to classic HDS desulfurization is the oxidative desulfurization of fuels and fuels.
  • a process is known in which sulfur-containing fuel oil with a water-soluble organic acid, such as acetic acid or formic acid, optionally additionally with a supported on a metal oxide transition metal oxidation catalyst or a carbonaceous promoter, and oxygen is contacted under elevated temperature and elevated pressure in a first reaction mixture to create a first oxidized mixture.
  • water is added to provide a biphasic mixture comprising a water rich phase and a fuel oil rich phase.
  • the water rich phase is separated from the fuel oil rich phase to create a purified fuel oil.
  • At least one oxidized sulfur compound may be separated from the first oxidized mixture using a solid-liquid extraction process, for example by an adsorption process, or using a liquid-liquid extraction process to obtain the purified fuel oil.
  • a solid-liquid extraction process for example by an adsorption process, or using a liquid-liquid extraction process to obtain the purified fuel oil.
  • the catalyst may be a vanadium-containing polyoxometalate catalyst having a keggin structure.
  • the catalyst is supported on HNO 3 pretreated alumina as the carrier material and is brought into contact with the diesel in this form.
  • the catalyst at the end of its efficacy, can be heat-treated at 250 ° C under a stream of air, i. H. apart from the diesel, to be regenerated.
  • US 2010/0300938 A1 discloses a process for the oxidative desulfurization of a sulfur-containing hydrocarbon mixture.
  • the hydrocarbon mixture is contacted with an aqueous oxidizing agent, such as hydrogen peroxide, in the presence of a catalyst for a time sufficient to oxidize at least a portion of the sulfur compounds in the hydrocarbon mixture.
  • the catalyst can is a polyoxometalate with a keggin structure.
  • the oxidized sulfur compounds are removed from the hydrocarbon mixture by a liquid-liquid extraction by means of a polar solvent, for example by means of methanol, acetonitrile or a mixture of 90 parts of acetonitrile and 10 parts of water.
  • the acetonitrile or the methanol can also be used to transfer large quantities of aromatic components from the hydrocarbon mixture into the polar solvent.
  • the hydrocarbon mixture is purified by means of an adsorbent to remove remaining sulfur compounds. It is believed that the sulfur compounds to be removed thereby are sulfur compounds poorly soluble in the polar solvent, such as sulfones.
  • the object of the present invention is to provide a method for producing desulphurised fuels that is improved over the prior art.
  • the object is solved by the features of patent claim 1. Embodiments result from the features of claims 2 to 14.
  • a second object of the invention is to provide a desulfurization apparatus which is suitable for carrying out such an improved process. This second object is solved by the features of claim 15.
  • the first object of the invention is achieved according to the invention by a process for the oxidative desulfurization of liquid fuels, wherein a reaction system comprising a fluid containing a homogeneous polyoxometalate catalyst as a first phase and a liquid containing organic sulfur compounds is provided as a second phase, wherein the the first phase and the second phase are mixed to form a phase interface, wherein the organic sulfur compounds contained in the second phase are catalytically converted at the phase interface to oxidation products, and wherein the sulfur-containing oxidation products be transferred from the phase interface in the first phase, whereby the second phase depleted of sulfur.
  • the fluid of the first phase is water. Addition of another solvent and / or excipient to the first phase is not required to carry out the process.
  • the polyoxometalate catalyst is regenerated by oxygen by metering oxygen into the reaction system in molecular form, ie in gaseous form, and by re-oxidizing the polyoxometalate catalyst dissolved in the first phase
  • a fluid containing a homogeneous polyoxometalate catalyst is understood in particular to mean a fluid having a dissolved polyoxometalate catalyst.
  • a liquid fuel containing organic sulfur compounds is understood in particular to mean a fuel in which the organic sulfur compounds are present in dissolved form.
  • the organic sulfur compounds contained in the second phase also include oxidized intermediates of the originally contained organic sulfur compounds, which are further oxidized in the course of the process. The oxidation products are thereby transferred from the phase boundary to the first phase, that they dissolve in the first phase. It is therefore a passive process. In order for this to happen and thereby deprive the second phase of sulfur, the catalytic conversion to oxidation products that takes place before must take place until water-soluble sulfur compounds are formed.
  • Sulfur which is depleted in the second phase, is therefore a water-soluble sulfur compound.
  • a fuel having an ultra-low sulfur content ie, a sulfur content of below 10 ppmw
  • the water-soluble sulfur compounds include in particular sulfate (SO 4 2 " ).
  • SO 4 2 " sulfate
  • the extraction is based on the mass transfer or the mass transfer at the phase interface between two immiscible phases, wherein in one of the two phases dissolved components with the aid of the second phase, the extractant are dissolved out. This requires - in addition to the mutual insolubility of the phases into each other - the solubility of the components to be extracted in the phase used as extractant.
  • the invention is based on the consideration that, when using such an extractive separation process, the desulfurization of a liquid fuel would require the use of an extractant which is immiscible with the fuel and at the same time enables the mass transfer of the organic sulfur compounds present in the fuel , Since fuels are nonpolar, this is basically suitable as a means of extraction, a polar and thus not soluble in the fuel fluid.
  • the problem here is that the organic sulfur compounds contained in fuels, such as thiophenes, thiophene derivatives or sulfides, also do not dissolve in such a polar solvent.
  • the invention now surprisingly recognizes, in a third step, that separation of the organic sulfur compounds present in a liquid fuel is possible if the organic sulfur compounds present in the fuel are converted in advance into products soluble in the phase used as the extraction agent become.
  • This is achieved in the two-phase reaction system according to the invention by the use of a homogeneous polyoxometalate catalyst in the first phase.
  • the polyoxometalate catalyst catalytically converts the organic sulfur compounds contained in the second phase at the phase interface between the first phase and the second phase to oxidation products.
  • oxidation is carried out until essentially all the sulfur compounds present in the fuel have been converted to water-soluble sulfur compounds.
  • a subsequent purification by a solid phase extraction or extraction by means of methanol, acetonitrile or other organic solvents is not required.
  • Such an organic solvent would have the disadvantage of also extracting aromatic components from the liquid fuel of the second phase.
  • the re-oxidation of the catalyst is not carried out by consumable hydrogen peroxide but by oxygen in molecular form, which can be added as needed, to the originally contained but also as intermediates To be formed, the resulting sulfur compounds oxidize until essentially only water-soluble sulfur compounds, such as sulfate or sulfonic acids, are present.
  • the oxidation products formed in the catalytic reaction are soluble in the first phase and there is a mass transfer between the two phases.
  • the oxidation products are converted from the phase interface into the first phase, whereby the second phase depleted of sulfur.
  • the process according to the invention thus also differs substantially from the process known from de Angelis, A. et al., Pure Applied Chemistry, 2007, Volume 79, No. 11, pages 1887 to 1894, in which the catalyst is immobilized on a solid support is present and regenerated separately from the catalytic reaction at elevated temperature in an air stream.
  • the first phase and the second phase are not or at least not substantially soluble in each other.
  • the phase interface forming between the two phases can be regarded macroscopically as a surface in the unmixed state. During mixing, the phase interface between the two immiscible phases increases.
  • phase boundary surface results directly from the formation of a temporary emulsion in which one of the two phases forms small droplets which are finely distributed in the other of the two phases.
  • the phase interface is thus considered microscopically as the sum of all surfaces of the droplets formed.
  • Both the product formation, ie the catalytic conversion of the organic sulfur compounds to the oxidation products, and the phase transfer of the products formed during the reaction from the second phase to the first phase take place at the phase interface.
  • the formed oxidation products are transferred from the phase interface into the first phase or go on at the phase interface in the first phase.
  • the second phase depletes sulfur during this process.
  • the liquid fuel is essentially free of sulfur or of the undesired organic sulfur-containing compounds.
  • the desulphurised fuel then meets the requirements of the limit values and can be used accordingly.
  • the above-described process steps of contacting the two phases, the thorough mixing, the catalytic oxidation of the organic sulfur compounds and the mass transfer of the formed oxidation products can be carried out at the phase interface in a common reaction device.
  • the product formation and the product separation can take place in a common process step.
  • Additional apparatuses and / or process steps for separating the oxidation products can be dispensed with.
  • the formed oxidation products are extracted by the fluid of the first phase and thus removed in an integrated separation step from the second phase, the liquid fuel.
  • the organic sulfur compounds present in the second phase selectively to oxidation products soluble in the first phase, in particular Sul- Fate, sulfonic acids and carboxylic acids, implement and thus targeted to remove from the fuel.
  • polyoxometalate catalyst is used.
  • Polyoxonetallates are complex compounds of light transition metals with oxygen. These metal-oxo anion clusters can also contain a large number of heteroatoms.
  • the metal atoms are usually transition metals, in particular vanadium, niobium, tantalum, molybdenum and tungsten.
  • the Polyoxonnetallate can in
  • Heteropolyanions and isopolyanions are subdivided. Heteropolyanions can contain additional heteroatoms, such as, for example, phosphorus (P), arsenic (As), silicon (Si) or germanium (Ge). Isopolyanions are pure metal oxide networks without heteroatoms. Form hydrogen together with azide
  • Polyoxonnetallate heteropolyacids or isopolyacids, which are used as catalysts.
  • the oxidation of the organic sulfur compounds takes place by an oxygen transfer from the polyoxometalate catalyst to the organic sulfur compounds.
  • the polyoxometalate catalyst in its oxidized form thus serves as an oxidant for the organic sulfur compounds.
  • the oxidation usually takes place at the phase interface between the first phase and the second phase during the mixing of the two phases.
  • a vanadium-containing polyoxometalate catalyst is used.
  • a polyoxometalate catalyst such with a
  • Polyoxometalat ion of the general formula [PMo x V y O 4 o] n ⁇ (HPA-y) are used.
  • HPA-y denotes a heteropoly acid here.
  • the polyoxometalate catalyst may consist of phosphorus (P), molybdenum (Mo), vanadium (V) and oxygen (O).
  • the indices n, x, y assume integer values in the following ranges: 5 ⁇ x ⁇ 12, 0 ⁇ y ⁇ 7 and 3 ⁇ n ⁇ 10.
  • x + y 12.
  • Water is used as the fluid of the first phase.
  • the liquid fuel (second phase) is usually nonpolar.
  • the organic sulfur compounds are accordingly soluble only in the second phase, the liquid fuel, but not in the first phase.
  • These are soluble in the first phase, but not in the second phase.
  • organic sulfur compounds thiophenes, their derivatives, benzothiophenes, their derivatives, sulfides, disulfides and / or thiols can be catalytically oxidized to the oxidation products.
  • the process also allows for the oxidation of less reactive sulfur compounds, such as dibenzothiophenes and 4,6-dialkyldibenzothiophene (4,6-DADBT), such as those found in vacuum resid oils and tar sands.
  • oxidation products sulfates, organic sulfonic acids and / or carboxylic acids can be formed. These oxidation products are polar and soluble in the first phase fluid.
  • carboxylic acids in particular
  • short-chain carboxylic acids such as formic acid or acetic acid formed.
  • Formed sulfate (SO 2 " ) can accumulate in the first phase in the form of sulfuric acid (H 2 SO) or hydrogen sulfate (HSO 4 " ).
  • H 2 SO sulfuric acid
  • HSO 4 " hydrogen sulfate
  • the sulfur depleted second phase is withdrawn for further use.
  • the sulfur content of the liquid fuel can be lowered so much that this under adherence to the predetermined limits as a liquid fuel, for example for driving Means of transport such as motor vehicles, aircraft and ships.
  • the oxidation products from the first phase can be separated.
  • separation processes such as precipitation, ion exchange, extraction or membrane processes.
  • the oxygen can be metered into the reaction system in the form of a gas mixture, in particular air or compressed air, and the catalyst dissolved in the first phase can be correspondingly re-oxidized.
  • the polyoxometalate catalyst is again available for the catalytic conversion of organic sulfur compounds contained in a fuel.
  • the regeneration of the polyoxometalate catalyst is simultaneous to the oxidation of the organic sulfur compound.
  • the term simultaneously means in the present case that the oxygen necessary for the regeneration of the catalyst is added to the reaction system already during the oxidation of the organic sulfur compounds.
  • the desulfurization of the fuel and the regeneration of the catalyst thus occur in one process step and thus under the same conditions, such. B. pressure and temperature.
  • liquid fuels can be desulfurized.
  • liquid fossil fuels ie fuels from fossil fuels
  • the fossil fuels are usually derived from oil or coal. These include, in particular, gasoline, diesel, kerosene and fuel oil, as well as lubricants derived from petroleum or coal.
  • biofuels can be desulfurized from renewable raw materials, ie vegetable origin, as liquid fuels. This includes, for example, rapeseed oil and biodiesel (rapeseed methyl ester, RME).
  • the catalytic reaction of the organic sulfur compounds to the oxidation products takes place at a temperature in a range between 70 ° C and 180 ° C, in particular at a temperature in a range between 90 ° C and 140 ° C.
  • the catalytic conversion of the organic sulfur compounds to the oxidation products can at a pressure in a range between 1 bar and 100 bar, in particular at a pressure in a range between 1 bar and 50 bar, in particular at a pressure in a range between 1, 5 bar and 20 bar, are performed.
  • the pressure may be the total gas pressure or the partial pressure of the oxygen in molecular form.
  • the process allows desulfurization of a liquid fuel having a relative sulfur content in a range between 500 ppmw and 12,000 ppmw.
  • the unit ppmw (parts per million weight) indicates the sulfur content in a fuel or in a liquid fuel in millionths of the total mass.
  • the fuel is depleted of sulfur to such an extent that it meets the requirements for the limit values required for use.
  • the process according to the invention can be carried out both continuously and batchwise, ie. H. in a batch process.
  • the second object of the invention is achieved according to the invention by a desulfurization device for liquid fuels, for carrying out the method according to one of the above-described embodiments, comprising a reaction vessel, a first feed for a homogeneous polyoxometalate catalyst-containing fluid as a first phase, a second Feed for a liquid containing organic sulfur compounds as a second phase, and an agitator for mixing the first phase and the second phase within the reaction vessel.
  • the desulfurization device comprises a feed line for oxygen in molecular form, in particular in the form of a gas mixture, such as. As air, for the regeneration of the homogeneous polyoxometalate catalyst.
  • the feed line is connected to the reaction vessel of the desulfurization device.
  • the desulfurization device according to the invention is set up and designed in particular for carrying out the method according to the invention.
  • the second inlet is used to supply the second phase, that is, the organic sulfur compounds containing liquid fuel.
  • Both phases are intensively mixed within the reaction vessel, whereby a large mass transfer area required for the mass transfer between the two phases is formed.
  • the organic sulfur compounds contained in the second phase are oxidized by the polyoxonetalate catalyst and thus converted into soluble in the first phase of the oxidation products.
  • the mass transfer takes place, the oxidation products are transferred to the first phase.
  • the second phase ie the liquid fuel, is thereby desulfurized.
  • the desulphurisation device comprises a first outlet for removing the first phase.
  • the first sequence is usually arranged on the reaction vessel.
  • the oxidation products dissolved in the first phase can be fed to a treatment device and separated there from the first phase.
  • the desulfurization device comprises a second outlet for removing the sulfur-depleted second phase.
  • the second sequence is arranged on the reaction vessel. The second phase is fed to its further use after the removal of the organic sulfur compounds.
  • a sulfur elemental analyzer from Antek was used. Analysis of the first phase of the catalyst was carried out by means of NMR spectroscopy (short-chain carboxylic acids), atomic emission spectroscopy (ICP-OES), and ion chromatography (IC). Gaseous products (CO 2 and CO from the sulfur compound) were detected by gas chromatography. The mass balances for carbon (C) and sulfur (S) could be concluded with the help of the analytics used. Depending on the type of sulfur compound used, up to 90% of the sulfur was converted from the second phase to the first phase as sulfate or sulfonic acid. Additionally, to study the distribution and behavior of the
  • FIG. 1 shows a schematic desulfurization device 1 for liquid fuels, in particular fuels.
  • the desulfurization device 1 comprises a reaction vessel 3, in which both the desulphurisation of a fuel and the separation of the products formed during the desulfurization takes place.
  • the reaction vessel 3 is formed as a high-pressure autoclave.
  • a fluid containing a homogeneous polyoxometalate catalyst is metered as the first phase 5 into the reaction vessel 3 via a first inlet 7.
  • 0.9 g of the polyoxometalate catalyst 4 H 8 [PMo7V 5 O] are dissolved in 200 ml of water.
  • a second phase 9 in the present case 3.36 g of benzothiophene dissolved in 69 g of isooctane, is metered in as the liquid fuel or fuel.
  • the inlets 7, 11 are only indicated diagrammatically by arrows.
  • High pressure autoclave 3 mixed at 1000 rpm for a period of 24 hours at a temperature of 140 ° C and an oxygen partial pressure of 20 bar.
  • a stirrer 17 is used for mixing.
  • phase boundary surface 15 between the immiscible phases 5, 9 no longer has a macroscopic surface, but increases markedly due to droplet formation, which increases the mass transfer area and thus improves mass transfer. This is not outlined here.
  • phase interface 15 both the product images and tion, ie the catalytic conversion of the organic sulfur compounds to the oxidation products, as well as the mass transfer of the products from the second phase 9 to the first phase 5 instead.
  • the formed oxidation products are transferred from the phase interface 15 into the first phase 5.
  • the second phase 9 depletes of sulfur during this process.
  • the reaction mixture is cooled to room temperature and the two phases 5, 9 separated.
  • the polar first phase 5 can be removed via a first outlet 19. If the first phase 5 is again used for the desulfurization of a liquid fuel, it remains in the high-pressure autoclave 3. Otherwise, the first phase 5 can be removed and the in the first phase 5 dissolved oxidation products are removed from this.
  • the sulfur depleted second phase 9 is removed from the high-pressure autoclave 3 via a second outlet 21.
  • the desulphurised fuel or fuel then meets the requirements of the specified limits and can continue to be used accordingly.
  • the regeneration of the dissolved in the first phase 5, homogeneous polyoxometalate catalyst is carried out by molecular oxygen or compressed air.
  • the regeneration of the polyoxometalate catalyst takes place here simultaneously to the oxidation of the organic sulfur compounds at the phase interface 15.
  • oxygen is added to the first phase 5 in molecular form, in particular in a diluted form, such as compressed air or synthetic air, and the catalyst is re-charged. oxidized. After the regeneration is the
  • Polyoxometalate catalyst again for the catalytic conversion of organic sulfur compounds available.
  • a two-phase reaction system consisting of a fuel with dissolved organic sulfur compounds as the second phase 9 and a polar first phase 5 having therein dissolved Polyoxonnetallat catalyst to selectively oxidize the organic Schwefelkomponen- to soluble in the first phase polar components and remove them targeted from the fuel.
  • gaseous by-products arise CO 2 and CO.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé pour la désulfuration par oxydation de carburants liquides, un système de réaction présentant un fluide contenant un catalyseur de type polyoxométallate homogène comme première phase (5) et un carburant liquide contenant des composés soufrés organiques comme deuxième phase (9) étant utilisé, la première phase (5) et la deuxième phase (9) étant mélangées avec formation d'une limite de phase (15), les composés soufrés organiques contenus dans la deuxième phase (9) étant transformés catalytiquement au niveau de la limite de phase (15) en produits d'oxydation et les produits d'oxydation étant transférés par la limite de phase (15) à la première phase (5), la deuxième phase (9) étant ainsi appauvrie en souffre. En outre, l'invention concerne un dispositif de désulfuration (1) pour carburants liquides qui est configuré et conçu pour la réalisation du procédé.
PCT/EP2017/053927 2016-02-26 2017-02-21 Procédé pour la désulfuration par oxydation de carburants liquides Ceased WO2017144460A1 (fr)

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DE102016203120.1 2016-02-26
DE102016203120.1A DE102016203120A1 (de) 2016-02-26 2016-02-26 Verfahren zur oxidativen Entschwefelung flüssiger Brennstoffe

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482841A1 (fr) * 1990-10-25 1992-04-29 The British Petroleum Company P.L.C. Désulfurisation d'huile
DE102009003659A1 (de) 2008-03-26 2009-10-15 General Electric Co. Oxidative Entschwefelung von Brennstofföl
US20100300938A1 (en) 2005-09-08 2010-12-02 Martinie Gary D Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US20130206646A1 (en) * 2010-11-01 2013-08-15 Yeda Research And Development Co., Ltd. Removal of heteroaromatic sulfides from hydrocarbons using polyoxometalates catalysts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482841A1 (fr) * 1990-10-25 1992-04-29 The British Petroleum Company P.L.C. Désulfurisation d'huile
US20100300938A1 (en) 2005-09-08 2010-12-02 Martinie Gary D Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
DE102009003659A1 (de) 2008-03-26 2009-10-15 General Electric Co. Oxidative Entschwefelung von Brennstofföl
US20130206646A1 (en) * 2010-11-01 2013-08-15 Yeda Research And Development Co., Ltd. Removal of heteroaromatic sulfides from hydrocarbons using polyoxometalates catalysts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ALBERTO DE ANGELIS ET AL: "HETEROPOLYACIDS AS EFFECTIVE CATALYSTS TO OBTAIN ZERO SULFUR DIESEL", PURE & APPLIED CHEMISTRY, PERGAMON PRESS, OXFORD, GB, vol. 79, no. 11, 31 December 2007 (2007-12-31), pages 1887 - 1894, XP002662680, ISSN: 0033-4545, DOI: 10.1351/PAC200779111887 *
ANGELIS, A. ET AL., PURE APPLIED CHEMISTRY, vol. 79, no. 11, 2007, pages 1887 - 1894
COLLINS F M ET AL: "OXIDATIVE DESULPHURISATION OF OILS VIA HYDROGEN PEROXIDE AND HETEROPOLYANION CATALYSIS", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 117, 1997, pages 397 - 403, XP001157535, ISSN: 1381-1169, DOI: 10.1016/S1381-1169(96)00251-8 *

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