EP1481037A1 - Distillate desulfurization process - Google Patents
Distillate desulfurization processInfo
- Publication number
- EP1481037A1 EP1481037A1 EP03711432A EP03711432A EP1481037A1 EP 1481037 A1 EP1481037 A1 EP 1481037A1 EP 03711432 A EP03711432 A EP 03711432A EP 03711432 A EP03711432 A EP 03711432A EP 1481037 A1 EP1481037 A1 EP 1481037A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- feedstock
- hydrogen
- hydrodesulfurization
- sulfur
- vaporization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Definitions
- the US Environmental Protection Agency is targeting a level of sulfur less than 15 ppm in 2006 for on-road diesel.
- the European Union specification will be less than 50 ppm in 2005.
- the World Wide Fuels Charter as supported by all global automobile manufacturers proposes even more stringent sulfur requirements of 5 to 10 ppm for the Category IV fuels for "advanced' countries.
- refiners will have to make fuels having even lower sulfur levels at the refinery gate.
- refiners are faced with the challenge of reducing the sulfur levels in fuels and in particular diesel fuel within the timeframes prescribed by the regulatory authorities.
- a hydrodesulfurization process is often employed to reduce the concentration of organosulfur compounds in hydrocarbons.
- the hydrodesulfurization is carried out by contacting a hydrocarbon feedstock with hydrogen at elevated temperatures and pressures in the presence of a hydrodesulfurization catalyst in order to convert the organosulfur compounds to hydrogen sulfide.
- a hydrodesulfurization catalyst in order to convert the organosulfur compounds to hydrogen sulfide.
- conventional hydrodesulfurization processes those skilled in the art typically will operate the reaction zone with a hydrogen circulation rate of approximately three times the chemical hydrogen consumption rate on a molar basis. This circulation rate is maintained in order to maintain the hydrogen partial pressure and avoid excessive increase in the concentration of hydrogen sulfide.
- the heavier the feedstock the greater the chemical hydrogen consumption rate and hence the desired hydrogen circulation rate.
- the circulation rate would generally be in the-range of about 600 to about 2000 standard cubic feet per barrel of feedstock ("SCFB").
- hydrodesulfurization processes including many multi-step processes.
- Typical reasons for using multi-step processes are that such processes permit the separation of liquid and vapor between stages, the use of a sulfur sensitive catalyst in a second stage, the improvement of color of diesel fuel with special second stage reaction conditions, the use of alternative reactor designs in the different stages, the hydrogenation of aromatics, the processing of heavier feedstocks, and the preparation of various specialty products other than low-sulfur fuel.
- U.S. Patent No. 6,171 ,477 B1 discloses a multi-step process that includes a desulfurization step with a heavy hydrocarbon feedstock having an initial boiling point of at least 360°C and a final boiling point of at least 500°C wherein the hydrogen circulation step is about 100 to about 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge (594 to 29,700 SCFB) with a most preferable charge of about 300 to about 500 Nm 3 /m3 (1782 to 2970 SCFB).
- This feedstock is a much heavier feedstock than the distillates used for diesel production, and consumes much more hydrogen and therefore requires much higher hydrogen circulation to supply hydrogen for consumption, to maintain hydrogen partial pressure, and to control buildup of hydrogen sulfide.
- U.S. Patent No. 5,403,470 discloses a two-stage process for improving the color of a diesel feedstock wherein the first hydrotreating stage is carried out to decrease the organosulfur content to less than 800 ppmw with a gas recycle rate of 400 to about 4000 standard cubic feet per barrel of feedstock. This process is a two-stage process in which the purpose of the second stage is to improve product color.
- U.S. Patent No. 5,316, 658 Ushio et al. discloses a two-stage process for the production of low sulfur diesel gas oil having a Saybolt color number of -10 or higher.
- hydrodesulfurization is carried out in the first stage at a hydrogen to oil ratio of 200 to about 5000 scf/bbl and more preferably 500 to 2000 scf/bbl.
- the purpose of the second stage is to improve the product color.
- U.S. Patent No. 5,068,025 discloses a two-stage process for the concomitant hydrogenation of aromatics and sulfur bearing hydrocarbons in a diesel boiling range hydrocarbon feedstock. The subject process discloses that the hydrogen feed rate will typically be 100 to about 5000 scf/bbl.
- U.S. Patent No. 4,431,526 discloses a two-stage process for hydroprocessing heavier feedstocks such as "hydrocarbon containing oils" including all liquid and liquid/vapor hydrocarbon mixtures such as crude petroleum oils and synthetic crudes, e.g.
- the hydrogen circulation rate is disclosed to be in the range of about 1000 to about 15,000 scf/bbl.
- U. S. Patent No. 5,114,562 discloses another two-stage process with inter-stage stripping wherein a middle distillate petroleum stream is hydrotreated to produce a low sulfur and low aromatic product.
- the second stage employs a sulfur sensitive noble metal catalyst to saturate the aromatics which saturation consumes hydrogen.
- the circulation rate in the first reaction zone is disclosed as ranging from 400 for light naphthas to 20,000 scf/bbl for cycle oils and preferably between 1,500 and 5,000 scf/bbl.
- the subject patent indicates that the average molecular weight of the feedstream is reduced by the virtue of the production of gasoline and LPG.
- U.S. Patent 3,147,210 discloses yet another two-stage hydrogenation process with inter-stage stripping, using a sulfur-sensitive noble metal catalyst in the second stage with a goal of high aromatics saturation.
- the hydrogen circulation rate is disclosed as ranging from 200 to 12,000 scf/bbl, preferably 1,000 to 8,000 scf/bbl for the hydrofining stage.
- the example discloses a circulate rate of 700 s.c.fJb for the hydrofining stage.
- Patent 6,251 ,262 B1 discloses a three-stage hydrodesufurization process for diesel gas oil wherein the hydrogen to oil ratio is about 1000 to about 5000 scf/bbl wherein a product having a sulfur content of 0.005 wt.% is recovered.
- U.S. Patent 5,110,444 discloses another three-stage process.
- This process uses three stages with counter current gas/liquid flow, inter-stage stripping, and noble metal catalysts in 2nd and 3rd stages.
- the patent refers to gas rates as high as 20,000 SCFB, with preferred range of 1,500 to 5,000 SCFB.
- the use of higher gas rates in the 2nd and/or 3rd stages accommodates the H 2 consumption engendered by aromatics saturation catalyzed by the noble metal catalysts.
- U.S. Patent No. 6,251 ,263 B1 discloses a three-reaction zone hydrogenation process that uses specific catalysts in specific ratios using hydrogen circulation rates of 1000 to 5000 scfb/ bbl. While the Patentees maintain they can reach deep desulfurization level of 0.0001 wt % (1 ppmw), the examples only disclose higher levels with Example 3 showing an effluent having 30 ppmw where the feedstock was a Middle East straight run gas oil.
- U.K. Patent 1,385,288 discloses a multi-stage process for the simultaneous production of a jet fuel and motor fuel which comprises passing a hydrocarbon oil into a hydrotreating zone and passing the effluent from the hydrotreating zone to a multistage hydrocracking zone.
- the patent discloses a hydrogen circulation rate of 1,000 to 50,000 SCFB. This is a hydrocracking process which cracks heavy feeds into lighter products and in so doing consumes much more hydrogen than a hydrodesulfurization process.
- the process of the present invention achieves deep desulfurization of distillate hydrocarbon feedstock to a level below 50 ppmw sulfur in a conventional hydrodesulfurization process reaction zone in the presence of a conventional hydrodesulfurization catalyst wherein the process is carried out at hydrogen circulation rate of at least 5 times the molar chemical hydrogen consumption rate and wherein the distillate feedstock is vaporized in the reaction zone to at least about 30 mole percent of the total feedstock.
- the process of the present invention involves carrying out the hydrodesulfurization process in a multistage process wherein at least one stage is carried out at conventional operating conditions including a conventional hydrogen circulation rate and a conventional feedstock vaporization wherein the more reactive sulfur compounds are removed and wherein at least one additional downstream stage is carried out at process conditions that include a hydrogen circulation rate of at least 5 times the chemical hydrogen consumption rate and wherein the distillate feedstock vaporization is at least about 30 mole percent of the total feedstock.
- FIG. 1 is a graph showing the relationship between desulfurization as achieved by the hydrodesulfurization process of the present invention versus the desulfurization achieved by a process employing the prior art hydrogen circulation rate and vaporization rate.
- the hydrocarbon feedstock suitable for use with the present inventioh generally comprises a substantial portion of a distillate hydrocarbon feedstock, wherein a "substantial portion" is defined as, for purposes of the present invention, at least 50% of the total feedstock by volume.
- the distillate hydrocarbon feedstock processed in the present invention consists essentially of any one, several, or all refinery streams boiling in a range from about 150°F to about 700°F, preferably 300°F to about 700°F, and more preferably between about 350°F and about 700°F at atmospheric pressure.
- the term "consisting essentially of is defined as at least 95% of the feedstock by volume.
- the lighter hydrocarbon components in the distillate product are generally more profitably recovered to gasoline and the presence of these lower boiling materials in distillate fuels is often constrained by distillate fuel flash point specifications.
- Heavier hydrocarbon components boiling above 700°F are generally more profitably processed as fluidized catalytic cracking process ("FCC") feed and converted to gasoline.
- FCC fluidized catalytic cracking process
- the presence of heavy hydrocarbon components in distillate fuels is further constrained by distillate fuel end point specifications.
- the distillate hydrocarbon feedstock can comprise high and low sulfur virgin distillates derived from high- and low-sulfur crudes, coker distillates, catalytic cracker light and heavy catalytic cycle oils, and distillate boiling range products from hydrocracker and resid hydrotreater facilities.
- coker distillate and the light and heavy catalytic cycle oils are the most highly aromatic feedstock components, ranging as high as 80% by weight (FIA).
- the majority of coker distillate and cycle oil aromatics are present as monoaromatics and di-aromatics with a smaller portion present as tri-aromatics.
- Virgin stocks such as high and low sulfur virgin distillates are lower in aromatics content ranging as high as 20% by weight aromatics (FIA).
- the aromatics content of a combined hydrogenation facility feedstock will range from about 5% by weight to about 80% by weight, more typically from about 10% by weight to about 70% by weight, and most typically from about 20% by weight to about 60% by weight.
- distillate hydrodesulfurization facility In a distillate hydrodesulfurization facility with limited operating capacity, it is generally preferable (most economical) to process feedstocks in order of highest aromaticity, since catalytic processes often proceed to equilibrium product aromatics concentrations. In this manner, maximum distillate pool dearomatization is generally achieved.
- the distillate hydrocarbon • feedstock sulfur concentration is generally a function of the high and low sulfur crude mix, the hydrodesulfurization capacity of a refinery per barrel of crude capacity, and the alternative dispositions of distillate hydrodesulfurization feedstock components.
- the higher sulfur distillate feedstock components are generally virgin distillates derived from high sulfur crude, coker distillates, and catalytic cycle oils from fluid catalytic cracking units processing relatively higher sulfur feedstocks.
- distillate feedstock components can range as high as 2% by weight elemental sulfur but generally range from about 0.1% by weight to about 0.9% by weight elemental sulfur.
- the distillate hydrocarbon feedstock nitrogen content is also generally a function of the nitrogen content of the crude oil, the hydrodesulfurization capacity of a refinery per barrel of crude capacity, and the alternative dispositions of distillate hydrodesulfurization feedstock components.
- the higher nitrogen distillate feedstocks are generally coker distillate and the catalytic cycle oils.
- These distillate feedstock components typically have total nitrogen concentrations ranging as high as 2,000 ppm, but generally range from about 1 ppm to about 900 ppm.
- the hydrodesulfurization process of the present invention generally begins with a distillate feedstock preheating step.
- the feedstock is preheated in feed/effluent heat exchangers prior to entering a furnace for final preheating to a targeted reaction zone inlet temperature that will assist in achieving the vaporization rate in accordance with the present invention.
- the feedstock can be contacted with a hydrogen stream prior to, during, and/or after preheating.
- the hydrogen stream can be pure hydrogen or can be in admixture with diluents such as low-boiling hydrocarbons, carbon monoxide, carbon dioxide, nitrogen, water, sulfur compounds, and the like.
- the hydrogen stream purity should be at least about 50% by volume hydrogen, preferably at least about 65% by volume hydrogen, and more preferably at least about 75% by volume hydrogen for best results.
- Hydrogen can be supplied from a hydrogen plant, a catalytic reforming facility, or other hydrogen-producing or hydrogen-recovery processes.
- the reaction zone can consist of one or more fixed bed reactors containing the same or different catalysts.
- a fixed bed reactor can also comprise a plurality of catalyst beds.
- the plurality of catalyst beds in a single fixed bed reactor can also comprise the same or different catalysts.
- the process of the present invention as explained in greater deal below, comprises a multi-stage process having more than one reaction zone.
- interstage cooling consisting of heat transfer devices between catalyst beds in the same reactor shell, can be employed. At least a portion of the heat generated from the hydrodesulfurization process can often be profitably recovered for use in the hydrodesulfurization process.
- a suitable heat sinks for absorbing such heat provided by the hydrodesulfurization reaction exotherm can and generally includes the feedstock preheat section of the hydrodesulfurization process upstream of the reactor preheat furnace described hereinabove. Where this heat recovery option is not available, cooling of the reaction zone effluent may be performed through cooling utilities such as cooling water or air, or through use of a hydrogen quench stream injected directly into the reactors.
- the reaction zone effluent is generally cooled and the effluent stream is directed to a separator device to remove the hydrogen. Some of the recovered hydrogen can be recycled back to the process while some of the hydrogen can be purged to external systems such as plant or refinery fuel.
- the hydrogen purge rate is often controlled to maintain a minimum hydrogen purity and to remove hydrogen sulfide.
- Recycled hydrogen is generally compressed, supplemented with "make-up" hydrogen, and reinjected into the process for further hydrodesulfurization. Hydrogen is preferably passed through the reaction zone or zones in a multi-stage process, in a co-current fashion.
- the separator device liquid effluent can then be processed in a stripper device where light hydrocarbons can be removed and directed to more appropriate hydrocarbon pools.
- the stripper liquid effluent product is then generally conveyed to blending facilities for production of finished distillate products.
- the hydrogen circulation rate be at least 5 times the chemical molar hydrogen consumption rate. It is preferable that the rate be at least 10 times the chemical molar hydrogen consumption rate and most preferably at least 20 times the chemical molar hydrogen consumption rate. For a typical distillate feedstock having a hydrogen consumption rate of 600 SCFB, these hydrogen circulation values correspond to 3,000 SCFB, 6,000 SCFB, and 12,000 SCFB, respectively.
- the percentage feedstock vaporization be at least 30 mole%, preferably at least 40 mole% and most preferably at least 50 mole%.
- the feedstock vaporization is a complex function of the feedstock boiling range and composition, reactor temperature, reactor pressure, and hydrogen circulation rate.
- Those skilled in the art can readily calculate the percentage vaporization or employ one of the commercially available software programs such as Hysis or PRO-ll to compute the percentage vaporization.
- the temperature, pressure, and circulation rate are predetermined refiners operate the hydrodesulfurization process at the percentage vaporization determined by the forgoing set conditions. Percentage vaporization in the hydrodesulfurization reaction zone is a dependent variable that the refiner generally does not monitor.
- the hydrogen circulation rate is used to manipulate the percentage vaporization and to set the vaporization at a desired level in accordance with the present invention.
- the percentage vaporization should be set at the high levels of the present invention in order to concentrate the sulfur reactants in the liquid phase and thereby accelerate their reaction.
- the hydrogen circulation rates required by the process of the present invention can be achieved by adding more compressors, or by running the compressors at greater severity, or by feeding less feedstock to increase the gas-to- oil ratio.
- the mole percent vaporization of feed is about 15% at about 1000 SCFB gas/oil circulation rate and about 25% at about 2000 SCFB gas/oil circulation rate.
- the feed vaporization is increased to at least 30 mole% by increasing gas/oil circulation rates to about 5000 SCFB, or higher for a typical feedstock.
- full vaporization of the feed typically occurs at gas rates of 10,000 to 20,000 SCFB.
- the hydrodesulfurization process is carried out in two or more-stages.
- the first stage or stages upstream of a stage operated at conditions in accordance with this invention can be operated at conventional operating conditions wherein the more reactive sulfur compounds are removed.
- At least one subsequent, downstream stage (or stages) is operated in accordance with conditions that include a hydrogen circulation rate of 5 times the chemical hydrogen consumption rate, preferably 10 times the chemical hydrogen consumption rate and most preferably 20 times the chemical hydrogen consumption rate.
- the conditions in the subsequent or downstream stage or stages also include a feedstock vaporization value of at least 30 mole%, preferably at least 40 mole%, and most preferably at least 50 mole%. Because not all of the stages are are exposed to the hydrogen circulation rates and feedstock vaporization rates of the present invention the multi-stage process minimizes overall capital cost, utility consumption and pressure drop.
- a new recycle loop can be added to feed extra gas to one or more of the stages.
- reaction zone temperature of from about 400°F to about 750°F, preferably from about 600°F to about 750°F, and most preferably from about 650°F to about 750°F for best results.
- Reaction temperatures below these ranges can result in less effective hydrodesulfurization. Excessively high temperatures can cause the process to reach a thermodynamic aromatic reduction limit, hydrocracking, catalyst deactivation, product instability, and increase energy costs.
- the process of the present invention generally operates at reaction zone pressures ranging from about 300 psig to about 2,000 psig, more preferably from about 500 psig to about 1,500 psig, and most preferably from about 600 psig to about 1,200 psig for best results.
- the process of the present invention generally operates at a liquid hourly space velocity (LHSV) of from about 0.2 hr. "1 to about 10.0 hr. "1 , preferably from about 0.5 hr. "1 to about 4.0 hr. "1 , and most preferably from about 1.0 hr. '1 to about 2.0 hr. "1 for best results.
- LHSV liquid hourly space velocity
- the remaining liquid phase has a very high concentration of the "difficult- to- desulfurize species.” This- means that the partial pressure of these sulfur species is increased inasmuch as the partial pressure is a function of the liquid mole fraction and the vapor pressure of the sulfur species.
- Ki xedphase ⁇ X order rate constant observed in mixed-phase operation K aporphm. - ⁇ order rate constant observed in all-vapor phase operation
- R, total pressure
- H molar flow rate of gas (excluding vaporized oil)
- M molar flow rate of oil
- the performance of conventional diesel desulfurization catalysts can be greatly enhanced by carrying out the hydrodesulfurization process in accordance with this invention.
- the effect is especially large with high-activity NiMo catalysts at deep desulfurization levels. Under these conditions, doubling the gas-to-oil rate can increase the apparent catalyst activity by 80%. In some cases, it is possible to more than triple the apparent catalyst activity by increasing the gas rate.
- the hydrodesulfurization catalysts used in the process of the present invention can be any conventional commercially available distillate hydrodesulfurization catalysts which comprise a hydrogenation component and a catalyst support.
- a hydrodesulfurization catalyst support component generally comprises a weakly acidic refractory inorganic oxide.
- the refractory inorganic oxide can be, but is not limited to catalytically active alumina, silica, and mixtures of silica and alumina with the preferred refractory inorganic oxide being catalytically active alumina.
- the catalytically active alumina can be gamma alumina, eta alumina, theta alumina, boehmite, or mixtures thereof with the preferred catalytically active alumina being gamma alumina.
- the hydrogenation component of a typical hydrodesulfurization catalyst comprises a Group VIB metal and a Group VIII metal of the Periodic Table of Elements.
- the Group VIB metals suitable for use in the present invention include chromium, molybdenum and tungsten.
- the preferred Group VIB metals are molybdenum and tungsten, and preferably molybdenum.
- the Group VIII metals suitable for use in the present invention include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
- the preferred Group VIII metals are cobalt and nickel, preferably nickel. These metals can be present in the catalyst in their elemental form or as their oxides, sulfides, or mixtures thereof.
- Hydrogenation component metals can be deposed or incorporated upon the support by impregnation employing heat-decomposable salts of the Group VIB and VIII metals or other methods known to those skilled in the art such as ion-exchange, with impregnation methods being preferred.
- Suitable aqueous impregnation solutions include, but are not limited to cobalt nitrate, ammonium molybdate, nickel nitrate, and ammonium meta-tungstate.
- Example 1 The FIG. 1 depicts a curve based on various hydrodesulfurization pilot plant runs carried out with a straight run light gas oil having the composition set forth in TABLE I. This feed had a chemical hydrogen consumption rate of 300 SCFB. Five pilot plant runs where carried in a pilot plant having a fixed bed reaction zone, operated isothermally with once-through hydrogen. Process conditions included 812 psig, 650°F, 2 LHSV. The catalyst was a conventional commercially available NiMo distillate hydrodesulfurization catalyst.
- the data point at 900 SCFB pertains to a run carried out in accordance with prior art process conditions, i.e. a hydrogen circulation to consumption ratio of 900:300 and a vaporization rate of less than 30 mble%.
- the data points at 3000 and 6000 SCFB pertain to runs carried out in accordance with the invention, i.e., hydrogen circulation to consumption ratios of 10, 10, and 20, respectively, and a vaporization rate of greater than 30 mole%.
- the mole% vaporization is 12% at 900 SCFB, 20% at 1500 SCFB, 37% at 3000 SCFB, and 62% at 6000 SCFB. From an inspection of FIG.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/093,567 US20030168383A1 (en) | 2002-03-06 | 2002-03-06 | Distillate desulfurization process |
US93567 | 2002-03-06 | ||
PCT/US2003/006821 WO2003076552A1 (en) | 2002-03-06 | 2003-03-05 | Distillate desulfurization process |
Publications (1)
Publication Number | Publication Date |
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EP1481037A1 true EP1481037A1 (en) | 2004-12-01 |
Family
ID=27788000
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03711432A Withdrawn EP1481037A1 (en) | 2002-03-06 | 2003-03-05 | Distillate desulfurization process |
Country Status (4)
Country | Link |
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US (1) | US20030168383A1 (en) |
EP (1) | EP1481037A1 (en) |
AU (1) | AU2003213744B2 (en) |
WO (1) | WO2003076552A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7674368B2 (en) | 2003-12-19 | 2010-03-09 | Shell Oil Company | Systems, methods, and catalysts for producing a crude product |
US20100098602A1 (en) | 2003-12-19 | 2010-04-22 | Opinder Kishan Bhan | Systems, methods, and catalysts for producing a crude product |
US7745369B2 (en) | 2003-12-19 | 2010-06-29 | Shell Oil Company | Method and catalyst for producing a crude product with minimal hydrogen uptake |
FR2872812B1 (en) * | 2004-07-12 | 2006-09-08 | Inst Francais Du Petrole | PROCESS FOR THE PRODUCTION OF ALKYL ESTERS OF FATTY ACIDS AND HIGH-PURITY GLYCERIN |
RU2007141712A (en) | 2005-04-11 | 2009-05-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | METHOD FOR PRODUCING SEMI-PRODUCT WITH REDUCED NITROGEN CONTENT AND CATALYST FOR ITS IMPLEMENTATION |
US7959795B2 (en) * | 2008-07-22 | 2011-06-14 | Exxonmobil Research And Engineering Company | Deep hydrodesulfurization of hydrocarbon feedstreams |
WO2010017618A1 (en) * | 2008-08-11 | 2010-02-18 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Gas-phase hydrotreating of middle-distillates hydrocarbon feedstocks |
US9765267B2 (en) | 2014-12-17 | 2017-09-19 | Exxonmobil Chemical Patents Inc. | Methods and systems for treating a hydrocarbon feed |
US11786893B2 (en) | 2019-03-01 | 2023-10-17 | United Laboratories International, Llc | Solvent system for cleaning fixed bed reactor catalyst in situ |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CA1295275C (en) * | 1986-12-04 | 1992-02-04 | Randall David Partridge | Process for increasing octane and reducing sulfur content of olefinic gasolines |
US5110444A (en) * | 1990-08-03 | 1992-05-05 | Uop | Multi-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
US5409596A (en) * | 1991-08-15 | 1995-04-25 | Mobil Oil Corporation | Hydrocarbon upgrading process |
AU658937B2 (en) * | 1991-11-19 | 1995-05-04 | Mobil Oil Corporation | Hydrocarbon upgrading process |
FR2805276B1 (en) * | 2000-02-23 | 2004-10-22 | Inst Francais Du Petrole | PROCESS FOR CONVERTING HYDROCARBONS ON A CATALYST WITH CONTROLLED ACIDITY |
-
2002
- 2002-03-06 US US10/093,567 patent/US20030168383A1/en not_active Abandoned
-
2003
- 2003-03-05 EP EP03711432A patent/EP1481037A1/en not_active Withdrawn
- 2003-03-05 AU AU2003213744A patent/AU2003213744B2/en not_active Ceased
- 2003-03-05 WO PCT/US2003/006821 patent/WO2003076552A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO03076552A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20030168383A1 (en) | 2003-09-11 |
WO2003076552A1 (en) | 2003-09-18 |
AU2003213744B2 (en) | 2008-06-26 |
AU2003213744A1 (en) | 2003-09-22 |
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