US3654139A - Desulphurisation and de-aromatisation of petroleum distillates - Google Patents
Desulphurisation and de-aromatisation of petroleum distillates Download PDFInfo
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- US3654139A US3654139A US742733A US3654139DA US3654139A US 3654139 A US3654139 A US 3654139A US 742733 A US742733 A US 742733A US 3654139D A US3654139D A US 3654139DA US 3654139 A US3654139 A US 3654139A
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- hydrogen
- sulphur
- nickel
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
Definitions
- This invention relates to the desulphurisation and dearomatisation of petroleum distillates boiling within the range 60 to 250 C.
- U.-K. Patent -No. 1,098,698 claims a process for the desulphurisation of a straight-run petroleum fraction containing up to 2.0% Wt. sulphur which comprises catalytically hydrodesulphurising the fraction in a first stage to convert the major proportion of the sulphur to hydrogen sulphide, removing the hydrogen sulphide, and contacting the fraction of reduced sulphur content with supported elemental nickel in a second stage under conditions such that residual sulphur is adsorbed by the nickel substantially without the liberation of hydrogen sulphide. Using this process sulphur levels can be reduced to 1 p.p.m. or less.
- the present invention combines a 2-stage desulphurisation similar to that of U.K. Patent No. 1,098,698 with a subsequent de-aromatisation process using a reduced nickel catalyst.
- a process for the desulphurisation and de-aromatisation of a pctroleum distillate boiling within the range 60 to 250 C. and containing up to 2% wt. sulphur and up to 25 wt. aromatics comprises catalytically hydrodesulphurising the distillate in a first stage to convert the major proportion of the sulphur to hydrogen sulphide, removing the hydrogen sulphide, contacting the fraction of reduced sulphur content with supported elemental nickel in a second stage under conditions such that residual suplphur is adsorbed by the nickel without substantial liberation of hy- Patented Apr. 4, 1972 drogen sulphide, without substantial hydrogenation of the aromatics and without substantial hydrocracking of the feedstock, and hydrogenating the aromatics in a third stage over supported elemental nickel.
- Any convenient petroleum fraction can be used, but de-aromatisation is particularly required with certain SBP solvents, white spirits and high quality kerosine used as illuminating oil.
- SBP solvents are produced to narrow boiling range specifications, e.g. 60-80 C., 60-90 0, -110" C. and -140 C.
- the feedstock can be fractionated into the required cuts either before or after processing according to the invention. If the whole feedstock is processed and then distilled only one distillation is necessary. If it is fractionated and the individual cuts processed, each cut must be individually stabilised.
- the present invention proposes a two-stage desulphurisation operation because it is diflicult, using conventional catalytic hydrodesulphurisation techniques, to remove last traces of sulphur from a feedstock. These traces of sulphur are likely to be ring-type compounds such a thiophenes and substituted thiophenes. Conventional hydrodesulphurisation involves conversion of the sulphur present to hydrogen sulphide, which is then removed, and ring-type compounds are more resistant to such treatment.
- Catalysts suitable for use in such a process can comprise one or more oxides or sulphides of elements of Groups VIa and VIII of the Periodic Table on a support comprising one or more refractory oxides selected from oxides of elements of Groups II to V of the Periodic Tables, for example cobalt and molybdenum oxides supported on alumina.
- the hydrogen sulphide produced during the catalytic hydrodesulphurisation stage is removed before the second desulphurisation stage so that the desulphurisation capacity of the nickel is not wasted on such easily removed sulphur.
- the majority of the hydrogen sulphide can be removed in the high pressure and low pressure separators which normally follow a catalytic hydrodesulphurisation reactor or zone.
- hydrogen sulphide can be removed by any of the known ways, for example by stripping with inert gas, by washing with caustic soda, by adsorption on an adsorbent such as zinc oxide, clay, or molecular sieves, or by treatment with a solvent such as glycol amine soltion.
- the product from the catalytic hydrodesulphurisation stage, free from hydrogen sulphide, is passed, in the second desulphurisation stage, over supported elemental nickel, which takes up residual sulphur and becomes progressively sulphided. It has been found that the presence of a small amount of hydrogen is beneficial even though the process is not a hydrodesulphurisation process because no hydrogen sulphide is produced.
- the hydrogen should of course be sulphur-free.
- the beneficial effect of hydrogen is believed to be due to the fact that the sulphur is present in organic sulphur compounds and that as the sulphur is adsorbed on the nickel unsaturated organic radicals are produced which tend to polymerise on the nickel surface and reduce its catalytic activity.
- hydrogen recycle is employed in the catalytic hydrodesulphurisation stage there will be no gaseous hydrogen efiluent from that stage. In this case it is desirable that hydrogen be supplied separately to the second stage in an amount to prevent deactivation.
- the amount of hydrogen supplied to the second stage should be controlled so that it is greater than the minimum necessary to prevent de-activation of the supported nickel, the maximum amount of hydrogen supplied depending on Whether the nickel is fresh, i.e. unsulphided, or other wise.
- the nickel may be regarded as fresh
- the inlet hydrogen to hydrocarbon ratio (based on total feed) should not exceed 0.3:1 molar.
- the inlet hydrogenzhydrocarbon ratio based on total feed should not at any time exceed :1 molar.
- the inlet hydrogen-hydrcarbon ratio should be 0.001 to 0.221 molar.
- the feedstock to the second stage can be in the vapour or liquid phase depending on whether or not the nickel is sulphided, the criterion being the above sulphurznickel ratio of 0.06:1 atomic.
- the feedstock should be in the liquid phase, the amount of hydrogen supplied being limited to that which will saturate the feedstock at the operating temperature and pressure. In this situation there will be substantially no hydrogen partial pressure.
- the amount of hydrogen supplied may be increased so that a hydrogen partial pressure exists,.
- the feedstocks in this latter case can be vapour or liquid, although liquid phase operation is preferred. When operating in liquid phase upward flow of the feedstock is desirable.
- the solubility of hydrogen in the feedstock will depend on the nature of the feedstock, the ambient temperature and the ambient pressure.
- the following table shows the effect of increasing pressure within the range 100-1000 p.s.i.a. on the solubility of two pure paraffin hydrocarbons at a primary hydrogen-hydrocarbon ratio of 0.1 :1 molar.
- the table shows that the phase conditions change more readily at lower pressures and with lower boiling components.
- the feedstock will be a relatively complex mixture of components of different carbon number and molecular type and the effect of changes in reaction conditions will also be complex.
- reaction condi- 4 tions are carefully chosen in relation to the nature of the feedstock it is possible to avoid a hydrogen vapour pressure in the system when the catalyst is fresh.
- Naphthenes can be added to the second stage feedstock if the aromatic content of the feedstock is high, i.e. greater than 15% Wt. This is to avoid the rapid absorption of hydrogen that would result from the hydrogenation of such an amount of aromatic hydrocarbons, which might cause a considerable variation in the concentration of hydrogen present, and an excessive temperature rise. Naphthene addition can be by direct addition of suitable material or, more conveniently, by recycle from the third (bydrogenation) stage of the present process.
- the temperature and pressure must be considered in relation to the hydrogenzhydrocarbon ratio.
- it is desirable to operate the second stage at a fairly high temperature since the sulphur capacity and desulphurisation activity of the supported nickel catalyst increase with temperature.
- the upper limit of temperature is set by the onset of sidereactions such as cracking, isomerisation, and possible ring opening, the first of these being the most important.
- the space velocity of the second stage will depend on the amount of sulphur present and the level to which it is to be reduced, but subject to these requirements it should desirably be as high as possible.
- reaction conditions other than the inlet hydrogenzhydrocarbon ratio, can be selected from the following ranges.
- the sulphur content of the first stage product will depend on the original sulphur content and boiling range of the feedstock and on the hydrocatalytic desulphurisation conditions. Preferably the sulphur content is reduced as much as possible in this first stage, thus increasing the life of the nickel in the second stage.
- the sulphur content of the first stage product should not exceed 50 p.p.m. wt., preferably not more than 10 p.p.m. wt.
- the second stage product preferably has a sulphur content of less than 1 p.p.m. wt. particularly less than 0.5 p.p.m. wt. and it may be below 0.1 p.p.m. wt.
- the sulphur contents quoted refer to both combined and uncombined sulphur, but are expressed as the element.
- the desulphurised product from the second stage is hydrogenated in the final stage of the process of the invention preferably in the vapour phase or mixed vapour/ liquid phase on entry to the final stage.
- the reaction conditions may be chosen from the following ranges.
- Liquid (product) recycle can be employed to control the third stage temperature, particularly if the aromatic content of the feedstock to the stage is greater than 5% wt.
- the use of liquid recycle means that the volume of material passing through the reactor is increased, and to achieve the same contact time, the use of a larger reactor would be necessary. If cooling is necessary this can alternatively be achieved by using a cooled tubular reactor, with the catalyst in the tubes and a cooling agent being passed over them. In this type of reactor a higher average catalyst bed temperature can be obtained for a given level of hydrogenation than is possible with an adiabatic reactor.
- any substance which is thermally stable within the temperature range of the process may be used as the cooling agent. If a cooled tubular reactor is used the third stage is preferably in the vapour phase throughout, as otherwise distribution difliculties may occur. If, however, product recycle is used the fact that this is in liquid phase at the reactor inlet means that the heat of vaporisation will assist the cooling effect and the minimum of liquid necessary to achieve the cooling effect may be used. This means that the total feed enters the final stage reactor at as low a temperature as possible, consistent with the temperature being high enough for the activity of the catalyst to be sufficient to hydrogenate the aromatics in the feedstock.
- the process conditions chosen from the above ranges will depend on the extent of hydrogenation (i.e. dearomatisation) required, which in turn will depend on the aromatic content of the feedstock to the stage and the type of product required.
- Certain types of SBP solvents for example may require aromatic contents of less than 100 ppm. wt. and this can be achieved with feedstocks to the process containing up to 25 wt. aromatics.
- With kerosines the initial aromatic content can be up to 25% wt., and reduction to an aromatic content of less than 1% wt. is practicable.
- the final stage temperature can be increased during processing as necessary to allow for decrease in catalyst activity with time.
- a product from the first (catalytic hydrodesulphurisation) stage is pumped by pump 2 to a saturator 21.
- Valves 15, 17, 18, 24 and 25 are closed.
- Excess hydrogen leaves saturator 21 via lines 22, 26 and 28.
- Valves 23 and 27 are open, the latter acting as a pressure control valve, and the excess gas is vented off, desirably being used in the other stages of the invention.
- the feed is saturated with hydrogen, and the feed, containing dissolved hydrogen only, then leaves via lines 4 and 6 and open valve to reactor 7, containing fresh catalyst. Liquid leaving reactor 7 goes via lines 8, 10 and 12 and open valve .11 to open valve 13 where it is flow-controlled out to the final stage via line 14, cooling taking place in condenser 9.
- the supported nickel catalyst used in the second and third stages can incorporate any of the known natural or synthetic support materials, such as the refractory oxides of elements of Groups II to V of the Periodic Table, or
- Sepiolite is the preferred material and the preferred catalyst for the second and third stages is nickel on sepiolite prepared and activated according to the disclosures of British Pat. No. 899,652.
- Sepiolite is the preferred support because it can withstand high temperatures under reducing or oxidising conditions, it holds the nickel in finely divided form and with a high surface area, and it is relatively cheap.
- the supported nickel catalyst preferably prepared and activated according to the above-mentioned British Pat. may contain from 1 to 50% wt. nickel (expressed as elemental nickel) and more particularly from 5 to 25% wt.
- Such a catalyst has high nickel surface area and has high activity and selectivity. We have found that it is capable of adsorbing sulphur up to a sulphurznickel atomic ratio of at least 0.75: 1. Since the sulphur capaacity of the support nickel material is high and is known it is possible to provide a sufficient amount of it to give an economic catalyst life.
- the hydrogen used in all stages of the process of the invention can be commercially pure or it may be a mixed gas derived from a refinery process such as steam reformer tail gas, also containing methane, or catalytic reformer off-gas. It should, however, be sulphurfree. Catalytic re former off-gas is preferred, since operation in the liquid phase enables comparatively high pressures to be used, and catalytic reformer olf-gass is available at approximately 400 p.s.i.g. Preferably the gas contains at least 50 mol percent hydrogen, and more particularly from 70 to 99 mol percent hydrogen.
- hydrogen may be supplied to each or every stage on a once-through or recycle basis. If a recycle method is used with a mixed gas, for example one containing methane, this can be removed by purging from the recycle gas or by separation from the liquid products.
- a recycle method is used with a mixed gas, for example one containing methane, this can be removed by purging from the recycle gas or by separation from the liquid products.
- EXAMPLE 1 (a) first stage: catalytic hydrodesulphurisation Standard cobalt oxide-molybdenum oxide on alumina catalyst was pretreated with hydrogen at 332 C. and then presulphided at 332 C. with carbon disulphide in n-heptane. A straight-run C 140 C. distillate fraction derived from a Kuwait crude and containing p.p.m. weight sulphur was desulphurised over this catalyst under the following conditions:
- the aromatic content of the distillate was 5 percent weight, comprising various quantities of C to C aromatics. No change in the aromatic content was detected by GLC analysis.
- EXAMPLE 2 (a) and (b) first and second stages: catalytic hydrodesulphurisation and desulphurisation over supported nickel A C 170 C. straight run distillate fraction was desulphurised over cobalt oxide-molybdenum oxide on alumina catalyst, using the operating conditions of Example 1(a). Thiophene was then added to increase the sulphur content to 22 p.p.m. weight. This material was then desulphurised over fresh wt. nickel on sepiolite in the liquid phase under the following conditions:
- the sulphur content of the product was 0.2 p.p.m. wt.
- the catalyst retained its activity after a period of 700 hours.
- EXAMPLE 3 (a) first stage: catalytic hydroesulphurisation The sulphur content of straight-run kerosine was reduced from 1700 p.p.m. wt. to 2.2 p.p.m. wt. by hydrodesulphurisation over cobalt oxide-molybdenum oxide on alumina catalyst,
- the aromatic content of the kerosine was 18% wt., as determined by infra-red spectroscopy. Use of this technique failed to detect any change in aromatic content after desulphurisation.
- a process for the desulphurisation and dearornatisation of petroleum distillate boiling Within the range 60 to 250 C. and containing up to 2% sulphur and up to 25% wt. aromatics which process comprises:
- step (b) removing the hydrogen sulphide from the product of step (a);
- the second stage being operated in the liquid phase with substantially all of the hydrogen present being dissolved in said distillate and with substantially no hydrogen partial pressure, when the catalyst has a sulphurznickel ratio of less than 0.06:1 atomic, the amount of hydrogen present being (a) not more than the maximum that would dissolve in said distillate at the stage temperature and pressure, and
- the second stage being operated in the liquid or the vapour phase and with a hydrogen partial pressure, when the catalyst has a sulphurznickel ratio equal to or in excess of 0.06:1 atomic, the amount of hydrogen present being (a) at a level at which a hydrogen vapour pressure exists at the stage temperature and pressure,
- distillate is a naphtha boiling within the range 60-170" C. or a white spirit boiling within the range 15 0l90 C. or a kerosine boiling within the range 180250 C.
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3177067 | 1967-07-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3654139A true US3654139A (en) | 1972-04-04 |
Family
ID=10328151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US742733A Expired - Lifetime US3654139A (en) | 1967-07-11 | 1968-07-05 | Desulphurisation and de-aromatisation of petroleum distillates |
Country Status (8)
Country | Link |
---|---|
US (1) | US3654139A (fr) |
AT (1) | AT284313B (fr) |
BE (1) | BE717938A (fr) |
DE (1) | DE1770834A1 (fr) |
FR (1) | FR1573585A (fr) |
GB (1) | GB1232594A (fr) |
NL (1) | NL6809779A (fr) |
NO (1) | NO121735B (fr) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3732155A (en) * | 1971-03-31 | 1973-05-08 | Exxon Research Engineering Co | Two-stage hydrodesulfurization process with hydrogen addition in the first stage |
US4849093A (en) * | 1987-02-02 | 1989-07-18 | Union Oil Company Of California | Catalytic aromatic saturation of hydrocarbons |
US5741414A (en) * | 1994-09-02 | 1998-04-21 | Nippon Oil Co., Ltd. | Method of manufacturing gas oil containing low amounts of sulfur and aromatic compounds |
US20030003331A1 (en) * | 2001-05-21 | 2003-01-02 | Dabbousi Bashir Osama | Liquid hydrocarbon based fuels for fuel cell on-board reformers |
JP2006104271A (ja) * | 2004-10-01 | 2006-04-20 | Nippon Oil Corp | 水素化精製軽油の製造方法、水素化精製軽油及び軽油組成物 |
WO2009070561A1 (fr) | 2007-11-30 | 2009-06-04 | Saudi Arabian Oil Company | Procédé pour produire de l'essence à faible teneur en soufre obtenue par craquage catalytique sans saturation de composés oléfiniques |
US20090145808A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Catalyst to attain low sulfur diesel |
US20090230026A1 (en) * | 2008-02-21 | 2009-09-17 | Saudi Arabian Oil Company | Catalyst To Attain Low Sulfur Gasoline |
US20110024330A1 (en) * | 2006-12-06 | 2011-02-03 | Saudi Arabian Oil Company | Composition and Process for the Removal of Sulfur from Middle Distillate Fuels |
WO2011061575A1 (fr) * | 2009-11-20 | 2011-05-26 | Total Raffinage Marketing | Procédé pour la production de fluides hydrocarbures ayant une faible teneur en aromatiques |
WO2011061576A1 (fr) * | 2009-11-20 | 2011-05-26 | Total Raffinage Marketing | Procédé pour la production de fluides hydrocarbures ayant une faible teneur en aromatiques |
US8535518B2 (en) | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
US9005432B2 (en) | 2010-06-29 | 2015-04-14 | Saudi Arabian Oil Company | Removal of sulfur compounds from petroleum stream |
US10246652B2 (en) | 2013-12-23 | 2019-04-02 | Total Marketing Services | Process for the dearomatization of petroleum cuts |
US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
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Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA958358A (en) * | 1969-12-31 | 1974-11-26 | Robert A. Johnson | Petroleum fractions of low ultraviolet absorbance |
NL153934B (nl) * | 1973-02-02 | 1977-07-15 | Basf Ag | Werkwijze voor de katalytische hydrogenering van aromaten, zwavel- en stikstofverbindingen bevattende minerale oliefracties. |
-
1967
- 1967-07-11 GB GB3177067A patent/GB1232594A/en not_active Expired
-
1968
- 1968-07-04 NO NO2674/68A patent/NO121735B/no unknown
- 1968-07-05 US US742733A patent/US3654139A/en not_active Expired - Lifetime
- 1968-07-10 DE DE19681770834 patent/DE1770834A1/de active Pending
- 1968-07-10 FR FR1573585D patent/FR1573585A/fr not_active Expired
- 1968-07-10 NL NL6809779A patent/NL6809779A/xx unknown
- 1968-07-11 AT AT669368A patent/AT284313B/de not_active IP Right Cessation
- 1968-07-11 BE BE717938D patent/BE717938A/xx unknown
Cited By (42)
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US3732155A (en) * | 1971-03-31 | 1973-05-08 | Exxon Research Engineering Co | Two-stage hydrodesulfurization process with hydrogen addition in the first stage |
US4849093A (en) * | 1987-02-02 | 1989-07-18 | Union Oil Company Of California | Catalytic aromatic saturation of hydrocarbons |
US5741414A (en) * | 1994-09-02 | 1998-04-21 | Nippon Oil Co., Ltd. | Method of manufacturing gas oil containing low amounts of sulfur and aromatic compounds |
US20030003331A1 (en) * | 2001-05-21 | 2003-01-02 | Dabbousi Bashir Osama | Liquid hydrocarbon based fuels for fuel cell on-board reformers |
US6884531B2 (en) | 2001-05-21 | 2005-04-26 | Saudi Arabian Oil Company | Liquid hydrocarbon based fuels for fuel cell on-board reformers |
JP2006104271A (ja) * | 2004-10-01 | 2006-04-20 | Nippon Oil Corp | 水素化精製軽油の製造方法、水素化精製軽油及び軽油組成物 |
EP1818385A1 (fr) * | 2004-10-01 | 2007-08-15 | Nippon Oil Corporation | Procédé de fabrication de gazole hydroraffiné, gazole hydroraffiné et composition de gazole |
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US20080308459A1 (en) * | 2004-10-01 | 2008-12-18 | Hideshi Iki | Process for Producing Hydrorefined Gas Oil, Hydrorefined Gas Oil, and Gas Oil Composition |
JP4643966B2 (ja) * | 2004-10-01 | 2011-03-02 | Jx日鉱日石エネルギー株式会社 | 水素化精製軽油の製造方法、水素化精製軽油及び軽油組成物 |
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US8323480B2 (en) | 2006-12-06 | 2012-12-04 | Saudi Arabian Oil Company | Composition and process for the removal of sulfur from middle distillate fuels |
US20090145807A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
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US20090145808A1 (en) * | 2007-11-30 | 2009-06-11 | Saudi Arabian Oil Company | Catalyst to attain low sulfur diesel |
US8142646B2 (en) | 2007-11-30 | 2012-03-27 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
US10596555B2 (en) | 2008-02-21 | 2020-03-24 | Saudi Arabian Oil Company | Catalyst to attain low sulfur gasoline |
US10252247B2 (en) | 2008-02-21 | 2019-04-09 | Saudi Arabian Oil Company | Catalyst to attain low sulfur gasoline |
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US20090230026A1 (en) * | 2008-02-21 | 2009-09-17 | Saudi Arabian Oil Company | Catalyst To Attain Low Sulfur Gasoline |
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WO2011061576A1 (fr) * | 2009-11-20 | 2011-05-26 | Total Raffinage Marketing | Procédé pour la production de fluides hydrocarbures ayant une faible teneur en aromatiques |
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CN102858921A (zh) * | 2009-11-20 | 2013-01-02 | 道达尔炼油与销售部 | 具有低芳族含量的烃流体的生产方法 |
US9005432B2 (en) | 2010-06-29 | 2015-04-14 | Saudi Arabian Oil Company | Removal of sulfur compounds from petroleum stream |
US9951283B2 (en) | 2011-01-19 | 2018-04-24 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
US8535518B2 (en) | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
US10246652B2 (en) | 2013-12-23 | 2019-04-02 | Total Marketing Services | Process for the dearomatization of petroleum cuts |
US10752847B2 (en) | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
US11149216B2 (en) | 2017-03-08 | 2021-10-19 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
US11149218B2 (en) | 2017-03-14 | 2021-10-19 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
US10975317B2 (en) | 2018-10-12 | 2021-04-13 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
US11230675B2 (en) | 2018-10-12 | 2022-01-25 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
Also Published As
Publication number | Publication date |
---|---|
AT284313B (de) | 1970-09-10 |
NO121735B (fr) | 1971-04-05 |
BE717938A (fr) | 1969-01-13 |
GB1232594A (fr) | 1971-05-19 |
FR1573585A (fr) | 1969-07-04 |
NL6809779A (fr) | 1969-01-14 |
DE1770834A1 (de) | 1972-01-13 |
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