WO2001081511A2 - Mazouts a faible teneur en soufre et composants aromatiques - Google Patents

Mazouts a faible teneur en soufre et composants aromatiques Download PDF

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Publication number
WO2001081511A2
WO2001081511A2 PCT/US2001/012520 US0112520W WO0181511A2 WO 2001081511 A2 WO2001081511 A2 WO 2001081511A2 US 0112520 W US0112520 W US 0112520W WO 0181511 A2 WO0181511 A2 WO 0181511A2
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WIPO (PCT)
Prior art keywords
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fuel composition
wppm
distillate fuel
sulfur level
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PCT/US2001/012520
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English (en)
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WO2001081511A3 (fr
Inventor
Edward Stanley Ellis
Lynne Gillespie
Michele Sue Touvelle
William Ernest Lewis
Gordon Frederick Stuntz
Lisa I-Ching Yeh
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Exxonmobil Research And Engineering Company
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Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to AU5166001A priority Critical patent/AU5166001A/xx
Priority to CA002405087A priority patent/CA2405087A1/fr
Priority to JP2001578585A priority patent/JP2004511579A/ja
Priority to AU2001251660A priority patent/AU2001251660B2/en
Priority to EP01925062A priority patent/EP1297100A4/fr
Publication of WO2001081511A2 publication Critical patent/WO2001081511A2/fr
Publication of WO2001081511A3 publication Critical patent/WO2001081511A3/fr
Priority to NO20025048A priority patent/NO20025048L/no

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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

  • the present invention relates to a distillate fuel composition boiling in the range of about 190°C to 400°C, and having a sulfur level of less than about 50 wppm, a total aromatics content of about 5 to 15 wt.%, a polynuclear aromatics content of less than about 1.5 wt.%, a total aromatics to polynuclear aromatics ratio of greater than about 11, a T10 boiling point greater than 200°C and an API gravity less than 43.
  • Diesel fuels are used widely in automotive transport largely due to their high fuel economy.
  • one of the problems when such fuels are burned in internal combustion engines is the pollutants in the exhaust gases that are emitted into the environment.
  • NOx oxides of nitrogen
  • particulate matter including inter alia soot, adsorbed hydrocarbons and sulfates
  • unburned hydrocarbons and to a lesser extent carbon monoxide.
  • sulfur dioxide emissions from diesel fuel exhaust gases are becoming increasingly a problem due to their affinity with after-treatment devices designed to reduce NOx and particulate emissions, thereby adversely affecting the functioning efficiency.
  • the oxides of sulfur have been reduced considerably by reducing the sulfur levels in the diesel itself through refining operations such as by hydrodesulfurization.
  • further advances are required to meet increasingly demanding worldwide legislation for progressively lower diesel powered vehicle exhaust emissions, especially NOx and particulate matter.
  • An established trade-off exists between the two pollutants, i.e. NOx and particulate matter, whereby an increase in one leads to a decrease in the other, for a given engine and operating conditions.
  • a typical example of such a scenario is U.S. 5,792,339 in which a diesel oil composition comprising 250-495 wppm sulfur, 5-8.6 wt. % of polynuclear aromatics (PNAs) and 10-23.9 wt. % total aromatics is disclosed.
  • PNAs polynuclear aromatics
  • Hydrotreating or in the case of sulfur removal, hydrodesulfurization, is well known in the art and typically requires treating the petroleum streams with hydrogen in the presence of a supported catalyst at hydrotreating conditions.
  • the catalyst is usually comprised of a Group VI metal with one or more Group VIII metals as promoters on a refractory support.
  • Cobalt promoted molybdenum on alumina catalysts are most widely used when the limiting specifications are hydrodesulfurization, while nickel promoted molybdenum on alumina catalysts are the most widely used for hydrodenitrogenation, partial aromatic saturation, as well as hydrodesulfurization.
  • U.S. Patent No. 5,389,111 teaches a diesel fuel composition having an aromatics content in the range from about 13 to 20 wt.%), a cetane number from about 54 to 60, which cetane number and aromatics content being within a certain area defined in Figure 1 of that patent.
  • U.S. Patent No. 5,389,112 teaches a low emissions diesel fuel composition having an aromatics content in the range of about 14.3 to 19.7 wt.%, a cetane number from about 53.4 to 60.8, which cetane number and aromatics content falls within a certain area of Figure 1 of that patent.
  • a distillate fuel composition boiling in the range of about 190°C to 400°C with a T10 point greater than 200°C, an API gravity less than 43, a sulfur level of less than about 50 wppm, a total aromatics content of about 5 to 15 wt.%, a polynuclear aromatics content of less than about 1.5 wt.%>, wherein the ratio of total aromatics to polynuclear aromatics is greater than about 11.
  • the sulfur level is less than about 25 wppm.
  • the total aromatics content is from about 10 to 15 wt.%>.
  • the polynuclear aromatics content is less than about 1.0 wt.%>.
  • the TI 0 boiling point is greater than about 200°C.
  • the API gravity is less than 43.
  • the ratio of total aromatics to polynuclear aromatics is greater than about 14.
  • the fuel is employed in a compression ignition (e.g., diesel) engine, preferably in order to abate NOx and particulate emissions therefrom. More preferably, the fuel is employed in an automotive diesel engine.
  • the invention is a fuel composition comprising a distillate boiling in the range of about 190°C to 400°C with a T10 point greater than 200°C, an API gravity less than 43, a sulfur level of less than about 50 wppm, a total aromatics content of about 5 to 15 wt.%>, a polynuclear aromatics content of less than about 1.5 wt.%, wherein the ratio of total aromatics to polynuclear aromatics is greater than about 11, to which is added at least one of (i) one or more lubricity aid, (ii) one or more viscosity modifier, (iii) one or more antioxidant, (iv) one or more cetane improver, (v) one or more dispersant, (vi)
  • Figure 1 hereof shows one preferred process scheme for producing the distillate fuel compositions of the present invention.
  • This process scheme shows two hydrodesulfurization stages and one aromatics saturation stage. Also shown in this figure is hydrogen-containing treat gas being cascaded from the downstream reaction stages to the upstream reaction stages.
  • Figure 2 hereof is a plot of the data relating to some properties of the products produced by the practice of this invention. Total aromatics content is plotted versus the ratio of total aromatics to polynuclear aromatics.
  • Feedstocks suitable for producing the low emissions distillate fuel compositions of this invention are those petroleum based feedstocks boiling in the distillate range and above. Such feedstocks typically have a boiling range from about 190 to about 400°C, preferably from about 200 to about 370°C. These feedstocks usually contain greater than about 3,000 wppm sulfur. Non-limiting examples of such feedstocks include virgin distillates, light cat cycle oils, light coker oils, etc. It is highly desirable for the refiner to upgrade these types of feedstocks by removing as much of the sulfur as possible, as well as to saturate aromatic compounds.
  • Figure 1 hereof One preferred process for producing the fuel products of the present invention is illustrated in Figure 1 hereof.
  • the process scheme shown in Figure 1 hereof offers an improvement over the prior art by using only once-through hydrogen treat gas in at least one of the stages.
  • the first hydrodesulfurization stage will reduce the levels of both sulfur and nitrogen, with sulfur levels being less than about 1,000 wppm, preferably to less than about 500 wppm.
  • the second hydrodesulfurization stage will reduce sulfur levels to less about 100 wppm.
  • the third stage, the aromatics hydrogenation stage will saturate a substantial amount of the aromatics.
  • the hydrogen in the treat gas reacts with impurities to convert them to H 2 S, NH 3; and water vapor, which are removed as part of the vapor effluent, and it also saturates olefins and aromatics.
  • FIG. 1 shows hydrodesulfurization reaction vessel Rl which contains reaction zones 12a and 12b, each of which is comprised of a bed of hydrodesulfurization catalyst. It will be understood that a this reaction stage can contain only one reaction zones or two or more reaction zones. It is preferred that the catalyst be in the reactor as a fixed bed, although other types of catalyst arrangements can be used, such as slurry or ebullating beds. Downstream of each reaction zone is a non-reaction zone, 14a and 14b. The non-reaction zone is typically void of catalyst, that is, it will be an empty section in the vessel with respect to catalyst.
  • liquid distribution means upstream of each reaction stage or catalyst bed.
  • the type of liquid distribution means is believed not to limit the practice of the present invention, but a tray arrangement is preferred, such as sieve trays, bubble cap trays, or trays with spray nozzles, chimneys, tubes, etc.
  • a vapor- liquid mixing device (not shown) can also be employed in non-reaction zone 14a for the purpose of introducing a quench fluid (liquid or vapor) for temperature control.
  • the feedstream is fed to reaction vessel Rl via line 10 along with a hydrogen-containing treat gas via line 16 that is cascaded from second hydrodesulfurization reaction stage R2.
  • cascaded when used in connection with a treat gas, means a stream of treat gas is separated from the vapor effluent of a first reaction stage and then conducted to the inlet of a second reaction stage without passing through a compressor.
  • the second reaction stage may be upstream or downstream of the first reaction stage with respect to liquid flow.
  • the relative reaction conditions in the first and second reaction stages and associated separation zones are regulated so that the treat gas in the vapor phase effluent from the first stage naturally flows to the second stage, without the need to increase the pressure of the treat gas in the first stage's vapor phase effluent.
  • all or a portion of the hydrogen-containing treat gas may also be conducted to hydrodesulfurization reaction stage Rl via line 18.
  • This additional hydrogen-containing treat gas will typically be cascaded or otherwise obtained from another refinery process unit, such as a naphtha hydrofmer.
  • the vapor effluent from S 1 may be (i) recycled via lines 20, 22, and 16, (ii) conducted away from the process via line 50, or (iii) used in a combination of (i) and (ii).
  • the term "recycled" when used herein regarding hydrogen treat gas is meant to indicate a stream of hydrogen-containing treat gas separated as a vapor effluent from one stage that passes through a gas compressor 23 to increase its pressure prior to being sent to the inlet of a reaction stage.
  • the compressor will also generally include a scrubber to remove undesirable species such as H 2 S from the hydrogen recycle stream.
  • the feedstream and hydrogen containing treat gas pass, co-currently, through the one or more reaction zones of hydrodesulfurization stage Rl to remove a substantial amount of the heteroatoms, preferably sulfur, from the feedstream.
  • the first hydrodesulfurization stage contain a catalyst comprised of Co-Mo, or Ni-Mo on a refractory support.
  • hydrodesulfurization refers to processes wherein a hydrogen-containing treat gas is used in the presence of a suitable catalyst which is primarily active for the removal of heteroatoms, preferably sulfur, and nitrogen, and for some hydrogenation of aromatics.
  • Suitable hydrodesulfurization catalysts for use in the reaction vessel Rl in the present invention include conventional hydrodesulfurization catalyst such as those that are comprised of at least one Group VIII metal, preferably Fe, Co or Ni, more preferably Co and/or Ni, and most preferably Co; and at least one Group VI metal, preferably Mo or W, more preferably Mo, on a relatively high surface area refractory support material, preferably alumina..
  • hydrodesulfurization catalyst supports include refractory oxides such as silica, zeolites, amorphous silica-alumina, and titania-alumina. Additives such as P can also be present. It is within the scope of the present invention that more than one type of hydrodesulfurization catalyst be used in the same reaction vessel and in the same reaction zone.
  • the Group VIII metal is typically present in an amount ranging from about 2 to 20 wt.%», preferably from about 4 to 15%.
  • the Group VI metal will typically be present in an amount ranging from about 5 to 50 wt.%, preferably from about 10 to 40 wt.%, and more preferably from about 20 to 30 wt.%). All metals weight percents are based on the weight of the catalyst.
  • Typical hydrodesulfurization temperatures range from about 200°C to about 400°C with a total pressures of about 50 psig to about 3,000 psig, preferably from about 100 psig to about 2,500 psig, and more preferably from about 150 to 500 psig. More preferred hydrogen partial pressures will be from about 50 to 2,000 psig, most preferably from about 75 to 800 psig.
  • a combined liquid phase/vapor phase product stream exits hydrodesulfurization stage Rl via line 24 and passed to separation zone SI wherein a liquid phase product stream is separated from a vapor phase product stream.
  • the liquid phase product stream will typically be one that has components boiling in the range from about 190°C to about 400°C, but will not have an upper boiling range greater than the feedstream.
  • the vapor phase product stream is collected overhead via line 20.
  • the liquid reaction product from separation zone SI is passed to hydrodesulfurization stage R2 via line 26 and is passed downwardly through the reaction zones 28a and 28b. Non-reaction zones are represented by 29a and 29b.
  • Hydrogen-containing treat gas is introduced into reaction stage R2 via line 30 that is cascaded from aromatics hydrogenation stage R3 and is passed cocurrent with the feedstock.
  • cascaded means that treat gas flows from a downstream reaction stage , such as the hydrogenation stage, to an upstream stage that is at the same or lower pressure, and thus there is no need for the gas to be compressed.
  • all or a portion of the treat gas may be added into R2 via line 32, which additional treat gas may be from another refinery process unit, such as a naphtha hydrofmer.
  • the rate of introduction of hydrogen contained in the treat gas be less than or equal to 3 times the chemical hydrogen consumption of this rate, more preferably less than about 2 times, and most preferably less than about 1.5 times.
  • the feedstream and hydrogen-containing treat gas pass, co-currently, through the one or more reaction zones of hydrodesulfurization stage R2 to remove a substantial amount of remaining sulfur, preferably to a level wherein the feedstream now has less than about 50 wppm sulfur, more preferably less than about 25 wppm sulfur.
  • Suitable hydrodesulfurization catalysts for use in the reaction vessel R2 in the present invention include conventional hydrodesulfurization catalyst such as those described for use in Rl.
  • Noble metal catalysts can also be employed, which is preferably selected from Pt and Pd or a combination thereof. Pt, Pd or the combination thereof is typically present in an amount ranging from about 0.5 to 5 wt.%, preferably from about 0.6 to 1 wt.%.
  • Typical hydrodesulfurization temperatures range from about 200°C to about 400°C with a total pressures of about 50 psig to about 3,000 psig, preferably from about 100 psig to about 2,500 psig, and more preferably from about 150 to 1,500 psig. More preferred hydrogen partial pressures will be from about 50 to 2,000 psig, most preferably from about 75 to 1,000 psig.
  • R2 outlet pressure ranges from about 500 to about 1000 psig.
  • reaction product from second hydrodesulfurization stage R2 is passed via line 38 to second separation zone S2 wherein a vapor product, containing hydrogen, is recovered overhead and passed to either, or both, of hydrodesulfurization stage Rl via lines 34 and 16, or for recycle via lines 34 and 35. Alternatively, all or a portion of S2's vapor product may be conducted away from the process.
  • the liquid fraction is passed to aromatics hydrogenation stage R3, via line 39 where it flows downward through reaction zones 36a and 36b.
  • Non-reaction zones, similar to those in R2 and R3, are represented by 37a and 37b.
  • said liquid fraction Prior to being passed downwardly through the reaction zones of R3, said liquid fraction can first be contacted in a stripping zone (not shown) to remove entrapped vapor components from the liquid stream.
  • a stripping zone (not shown) to remove entrapped vapor components from the liquid stream.
  • the liquid product stream flows through the stripping zone, it is contacted by upflowing hydrogen-containing treat gas under conditions effective for transferring at least a portion of the feed impurities (H 2 S and NH 3 ) from the liquid to the vapor. It is preferred that at least about 80%, more preferably at least about 90%> of the remaining H 2 S and NH 3 will be removed from the downflowing liquid stream.
  • the contacting means comprises any known vapor- liquid contacting means, such as rashig rings, berl saddles, wire mesh, ribbon, open honeycomb, gas-liquid contacting trays, such as bubble cap trays and other devices, etc. It is within the scope of this invention that the stripping zone may be part of reaction vessel R3 or it may be a separate vessel. It is to be understood that although the figure hereof shows the hydrogenation stage operated in countercurrent mode wherein treat gas flows countercurrent to the flow of feedstock, it is understood that the hydrogenation stage can be operated in cocurrent mode as well.
  • the treat gas rate is preferably from about 400 to 1,200 scf/bbl (standard cubic feet per barrel), more preferably from about 500 to 1,000 scf/bbl.
  • the introduction of clean treat gas allows reaction stage R3 to be operated more efficiently owing to a reduction in the activity suppression effects on the catalyst exerted by H 2 S and NH 3 and an increase in H 2 partial pressure. This type of multi- stage operation is particularly attractive for very deep removal of sulfur and nitrogen or when a more sensitive catalyst (i.e., hydrocracking, aromatic saturation, etc) is used in the second reactor.
  • the treat gas rate is relatively low compared with more conventional processes.
  • the use of relatively low treat gas rates is primarily due to the use of previously hydrotreated distillate feedstocks. Further efficiencies are gained by not requiring recycle of treat gas.
  • the treat gas used in R3 is a once-through treat gas.
  • the liquid stream and treat gas are passed countercurrent to each other through one or more catalyst beds, or reaction zones, 36a and 36b.
  • the resulting liquid product stream exits reaction stage R3 via line 42, and a hydrogen- containing vapor product stream exits reaction stage R3 and is cascaded to reaction stage R2 via line 30.
  • the catalyst used in the reaction zones of this second reaction stage can be any suitable aromatics saturation catalyst.
  • Non-limiting examples of aromatics hydrogenation catalysts include nickel, cobalt-molybdenum, nickel- molybdenum, nickel-tungsten, and noble metal containing catalysts. Preferred are the noble metal catalysts.
  • Non-limiting examples of noble metal catalysts include those based on platinum and/or palladium, which is preferably supported on a suitable support material, typically a refractory oxide material such as alumina, silica, alumina-silica, kieselguhr, diatomaceous earth, magnesia, and zirconia. Zeolitic supports can also be used. Such catalysts are typically susceptible to sulfur and nitrogen inhibition or poisoning.
  • the aromatic saturation stage is preferably operated at a temperature from about 40°C to about 400°C, more preferably from about 200°C to about 350°C, at a pressure from about 100 psig to about 3,000 psig, preferably from about 200 psig to about 1,200 psig, and at a liquid hourly space velocity (LHSV) of from about 0.3 V/V/Hr. to about 10 V/V/Hr, preferably from about 1 to 5 V/V/Hr.
  • LHSV liquid hourly space velocity
  • line 44 to R2 and line 46 to R3 can carry a quench fluid that may be either a liquid or a gas.
  • Hydrogen is a preferred gas quench fluid and kerosene is a preferred liquid quench fluid.
  • reaction stages used in the practice of the present invention are operated at suitable temperatures and pressures for the desired reaction, they are preferably regulated to provide for treat gas cascading from R2 and R3 to Rl, and for once-through treat gas in R2.
  • typical hydroprocessing temperatures will range from about 20°C to about 400°C at pressures from about 50 psig to about 3,000 psig
  • reaction conditions, particularly reaction pressures will generally be regulated to provide the desired treat gas flow to minimize or preferably eliminate the need for ancillary pressure regulation equipment, such as compressors.
  • the hydrogenation stage contain two or more reaction zones operated at different temperatures. That is, at least one of the reaction zones will be operated at a temperature at least 25 °C, preferably at least about 50°C cooler than the other zone(s). It is preferred that the last downstream reaction zone, with respect to the flow of feedstock be the reaction zone that it operated at the cooler temperatures.
  • hydroprocessing and in the context of the present invention, the terms "hydrogen” and “hydrogen-containing treat gas” are synonymous and may be either pure hydrogen or a hydrogen-containing treat gas which is a treat gas stream containing hydrogen in an amount at least sufficient for the intended reaction, plus other gas or gasses (e.g., nitrogen and light hydrocarbons such as methane) which will not adversely interfere with or affect either the reactions or the products.
  • gas or gasses e.g., nitrogen and light hydrocarbons such as methane
  • Impurities such as H2S and NH3 are undesirable and, if present in significant amounts, will normally be removed from the treat gas, before it is fed into the Rl reactor.
  • the treat gas stream introduced into a reaction stage will preferably contain at least about 50 vol.%> hydrogen, more preferably at least about 75 vol.% hydrogen, and most preferably at least 95 vol.% hydrogen.
  • unreacted hydrogen in the vapor effluent of any particular stage is used for hydroprocessing in any stage, there must be sufficient hydrogen present in the fresh treat gas introduced into that stage for the vapor effluent of that stage to contain sufficient hydrogen for the subsequent stage or stages.
  • all or a portion of the hydrogen required for the first stage hydroprocessing is contained in the second stage vapor effluent fed up into the first stage.
  • the first stage vapor effluent will be cooled to condense and recover the hydrotreated and relatively clean, heavier (e.g., C4+) hydrocarbons.
  • the liquid phase in the reaction vessels used in the present invention will typically be comprised of primarily the higher boiling point components of the feed.
  • the vapor phase will typically be a mixture of hydrogen-containing treat gas, heteroatom impurities like H 2 S and NH 3 , and vaporized lower-boiling components in the fresh feed, as well as light products of hydroprocessing reactions. If the vapor phase effluent still requires further hydroprocessing, it can be passed to a vapor phase reaction stage containing additional hydroprocessing catalyst and subjected to suitable hydroprocessing conditions for further reaction. Alternatively, the hydrocarbons in the vapor phase products can be condensed via cooling of the vapors, with the resulting condensate liquid being recycled to either of the reaction stages, if necessary. It is also within the scope of the present invention that a feedstock which already contains adequately low levels of heteroatoms be fed directly into the reaction stage for aromatic saturation and/or cracking.
  • distillate fuel products are characterized as having relatively low sulfur and polynuclear aromatics (PNAs) levels and a relatively high ratio of total aromatics to polynuclear aromatics.
  • PNAs polynuclear aromatics
  • Such distillate fuels may be employed in compression-ignition engines such as diesel engines, particularly so- call "lean-burn" diesel engines.
  • compression-ignition engines such as diesel engines, particularly so- call "lean-burn" diesel engines.
  • Such fuels are compatible with: compression- ignition engine systems such as automotive diesel systems utilizing (i) sulfur- sensitive NOx conversion exhaust catalysts, (ii) engine exhaust particulate emission reduction technology, including particulate traps, and (iii) combinations of (i) and (ii).
  • distillate fuels have moderate levels of total aromatics, reducing the cost of producing cleaner-burning diesel fuel and also reducing CO 2 emissions by minimizing the amount of hydrogen consumed in the process.
  • the distillate compositions of the present invention contain less than about 50 wppm, preferably less than about 25 wppm, more preferably less than about 10 wppm, and most preferably less than about 5 wppm sulfur. They will also have a total aromatics content from about 5 to 15 wt.%>, preferably from about 10 to 15 wt.%.
  • the PNA content of the distillate product compositions obtained by the practice of the present invention will be less than about 1.5 wt.%, preferably less than about 1.0 wt.%, and more preferably less than about 0.5 wt.%.
  • the aromatics to PNA ratio will be at least about 11, preferably at least about 14, and more preferably at least about 17. In another embodiment, the aromatics to PNA ratio ranges from 11 to about 50, preferably from 11 to about 30, and more preferably from 11 to about 20.
  • PNA polynuclear aromatics that are defined as aromatic species having two or more aromatic rings, including alkyl and olefin-substituted derivatives thereof.
  • Naphthalene and phenanthrene are examples of PNAs.
  • aromatics is meant to refer species containing one or more aromatic ring, including alkyl and olefin-substituted derivatives thereof.
  • naphthalene and phenanthrene are also considered aromatics along with benzene, toluene and tetrahydronaphthalene. It is desirable to reduce PNA content of the liquid product stream since PNAs contribute significantly to emissions in diesel engines. However, it is also desirable to minimize hydrogen consumption for economic reasons and to minimize CO 2 emissions associated with the manufacture of hydrogen via steam reforming. Thus, the current invention achieves both of these by obtaining a high aromatics to PNA ratio in the liquid product.
  • the fuels of the present invention boil in the range of about 190°C to
  • Fuels having a ratio of total aromatics/PNAs >11 can be prepared by blending large amounts of lighter materials which contain single ring aromatics, but few PNAs.
  • the fuels of the present invention are also distinguished from these in that the T10 boiling point is greater than 200°C and the API gravity is less than 43.
  • the fuels may be combined with other distillate or upgraded distillate.
  • the products are compatible with effective amounts of fuel additives such as lubricity aids, cetane improvers, and the like. While a major amount of the product is preferably combined with a minor amount of the additive, the fuel additive maybe employed to an extent not impairing the performance of the fuel. While the specific amount(s) of any additive employed will vary depending on the use of the product, the amounts may generally range from 0.05 to 2.0 wt.%) based on the weight of the product and additive(s), although not limited to this range.
  • the additives can be used either singly or in combination as desired.
  • a virgin distillate feed containing from about 10,000 to 12,000 wppm sulfur was processed in a commercial hydrodesulfurization unit (first hydrodesulfurization stage) using a reactor containing both conventional commercial NiMo/ Al 2 O 3 (Akzo-Nobel KF842/840) and CoMo/Al 2 O 3 (Akzo-Nobel KF-752) catalyst under the following typical conditions: 300-350 psig; 150-180 psig outlet H 2 ; 75% H 2 treat gas; 500-700 SCF/B treat gas rate; 0.3-0.45 LHSV; 330-350°C.
  • Examples 1 - 3 demonstrate that products with less than 50 ppm S can be produced wherein the rate of introduction of hydrogen in the treat gas in the second reaction stage is less than or equal to three times the chemical hydrogen consumption. Examples 1-3 also demonstrate that products with 5-15 wt.% aromatics can be produced having a ratio of total aromatics to PNAs greater than about 11 and a T10 boiling point greater than 200°C.
  • Comparative Examples A-E are all conventional fuels with less than
  • Comparative examples A, B, C and D describe fuels that have total aromatics levels greater than 15 wt.% and all have a ratio of total aromatics to PNAs less than 10, which is outside the range of this invention.
  • Comparative example E is a Swedish Class 1 diesel which has a very low total aromatics level of less than 5 wt%> and a total aromatics to PNA ratio of greater than 25. Products with less than 5 wt.% total aromatics are outside the range of this invention. Table 2
  • the area inside the box in Figure 2 defines the products of this invention.
  • the total aromatics/PNA ratio can be greater than 30. Even though Figure 2's abscissa is truncated at 30 for clarity, it should be understood that the total aromatics/PNA ratio may exceed 30.
  • the preferred products of the invention have S levels less than about 50 wppm, a T10 boiling point greater than 200 °C, and an API gravity less than 43.
  • the designations "FIA”, "MS”, and “SFC” are well known in the art as analytical techniques. For example, “FIA” stands for fluorescence indicator analysis, “MS” stands for mass spectrophotometry; and “SFC” stands for supercritical fluid chromatography.
  • Table 3 provides additional comparative examples of distillate fuels that fall outside the range of this invention. These data were obtained from the following publications. -1 X. Li et al. "Comparison of the Exhaust Emissions of Diesel Fuels Derived From Oil Sands and Conventional Crude Oil,” SAE Technical Paper Series 982487, Oct. 19-22, 1998.
  • Example 4 The first one, Example 4, was prepared in a commercial hydrodesulfurization unit from a virgin distillate feed using a conventional CoMo/Al 2 O 3 catalyst and represents a typical commercial diesel fuel composition.
  • Example 5 is a composition according to the present invention. The properties of these two fuels are shown in Table 4 below.
  • the EPEFE program is based on an established set of equations from testing of 11 diesel fuels in 19 vehicles to predict the emissions performance of a fleet of vehicles based upon the fuel parameters: cetane No., density and polycyclic aromatic content.
  • cetane No. density and polycyclic aromatic content.
  • the EPEFE calculations would lead one to expect lower particulate matter and NOx emissions for the fuel of Example 5.
  • Table 5 show the average difference between the predicted reduction in emissions obtained from the EPEFE calculations and the observed reduction in average emissions for the fuel of Example 5 vs. the fuel of Example 4.
  • the data indicate that the reduction in NOx and particulate matter emissions achieved using the fuel compositions of the present invention (Example 5) were substantially greater than that predicted for any of the 19 vehicles used in the EPEFE program as well as being significantly lower than the EPEFE fleet average.
  • negative percentages indicate an emissions performance improvement.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne une composition de mazout dont le point d'ébullition varie de 190 °C à 400 °C avec un point T10 supérieur à 200 °C, une gravité API inférieure à 43, un niveau de soufre inférieur à environ 50 wppm, un contenu aromatique total d'environ 5 à 15 % en poids, un contenu aromatique polynucléaire inférieur à environ 1,5 % en poids, le rapport entre le total des composants aromatiques et les composants aromatiques polynucléaires étant supérieur à 11 environ.
PCT/US2001/012520 2000-04-20 2001-04-17 Mazouts a faible teneur en soufre et composants aromatiques WO2001081511A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU5166001A AU5166001A (en) 2000-04-20 2001-04-17 Low sulfur/low aromatics distillate fuels
CA002405087A CA2405087A1 (fr) 2000-04-20 2001-04-17 Mazouts a faible teneur en soufre et composants aromatiques
JP2001578585A JP2004511579A (ja) 2000-04-20 2001-04-17 低硫黄／低芳香族化合物留出油燃料
AU2001251660A AU2001251660B2 (en) 2000-04-20 2001-04-17 Low sulfur/low aromatics distillate fuels
EP01925062A EP1297100A4 (fr) 2000-04-20 2001-04-17 Mazouts a faible teneur en soufre et composants aromatiques
NO20025048A NO20025048L (no) 2000-04-20 2002-10-21 Destillat brennstoff med lavt innhold av svovel og aromater

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55337300A 2000-04-20 2000-04-20
US09/553,373 2000-04-20

Publications (2)

Publication Number Publication Date
WO2001081511A2 true WO2001081511A2 (fr) 2001-11-01
WO2001081511A3 WO2001081511A3 (fr) 2002-02-21

Family

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PCT/US2001/012520 WO2001081511A2 (fr) 2000-04-20 2001-04-17 Mazouts a faible teneur en soufre et composants aromatiques

Country Status (6)

Country Link
EP (1) EP1297100A4 (fr)
JP (1) JP2004511579A (fr)
AU (2) AU5166001A (fr)
CA (1) CA2405087A1 (fr)
NO (1) NO20025048L (fr)
WO (1) WO2001081511A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321504A3 (fr) * 2001-12-18 2003-10-22 Ethyl Corporation Compositions extrêmement stabiles de combustible pour moteurs Diesel.
US7345210B2 (en) 2004-06-29 2008-03-18 Conocophillips Company Blending for density specifications using Fischer-Tropsch diesel fuel
WO2016081217A1 (fr) * 2014-11-20 2016-05-26 Exxonmobil Research And Engineering Company Hydrotraitement pour la production de distillats
EP4198109A1 (fr) * 2021-12-18 2023-06-21 Indian Oil Corporation Limited Production de distillats désaromatisation à faible teneur en benzène pour des applications spéciales

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8361309B2 (en) * 2008-06-19 2013-01-29 Chevron U.S.A. Inc. Diesel composition and method of making the same
US9932945B2 (en) * 2009-12-18 2018-04-03 Chevron U.S.A. Inc. Method of reducing nitrogen oxide emissions

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US5389111A (en) * 1993-06-01 1995-02-14 Chevron Research And Technology Company Low emissions diesel fuel
US5389112A (en) * 1992-05-01 1995-02-14 Chevron Research And Technology Company Low emissions diesel fuel
US5792339A (en) * 1994-05-10 1998-08-11 Tosco Corporation Diesel fuel
US5976201A (en) * 1993-03-05 1999-11-02 Mobil Oil Corporation Low emissions diesel fuel
US6004361A (en) * 1993-03-05 1999-12-21 Mobil Oil Corporation Low emissions diesel fuel
US6150575A (en) * 1998-11-12 2000-11-21 Mobil Oil Corporation Diesel fuel

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US5807413A (en) * 1996-08-02 1998-09-15 Exxon Research And Engineering Company Synthetic diesel fuel with reduced particulate matter emissions
EP0856573A3 (fr) * 1997-01-29 2000-03-08 Kabushiki Kaisha Toyota Chuo Kenkyusho Composition de carburant diesel à émissions réduite de particules
JP3744672B2 (ja) * 1997-01-29 2006-02-15 株式会社豊田中央研究所 パティキュレート低減用軽油組成物
EP1835011A1 (fr) * 1998-10-05 2007-09-19 Sasol Technology (Pty) Ltd Distillats intermédiaires biodégradables et leur production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389112A (en) * 1992-05-01 1995-02-14 Chevron Research And Technology Company Low emissions diesel fuel
US5976201A (en) * 1993-03-05 1999-11-02 Mobil Oil Corporation Low emissions diesel fuel
US6004361A (en) * 1993-03-05 1999-12-21 Mobil Oil Corporation Low emissions diesel fuel
US5389111A (en) * 1993-06-01 1995-02-14 Chevron Research And Technology Company Low emissions diesel fuel
US5792339A (en) * 1994-05-10 1998-08-11 Tosco Corporation Diesel fuel
US6150575A (en) * 1998-11-12 2000-11-21 Mobil Oil Corporation Diesel fuel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321504A3 (fr) * 2001-12-18 2003-10-22 Ethyl Corporation Compositions extrêmement stabiles de combustible pour moteurs Diesel.
US7345210B2 (en) 2004-06-29 2008-03-18 Conocophillips Company Blending for density specifications using Fischer-Tropsch diesel fuel
WO2016081217A1 (fr) * 2014-11-20 2016-05-26 Exxonmobil Research And Engineering Company Hydrotraitement pour la production de distillats
EP4198109A1 (fr) * 2021-12-18 2023-06-21 Indian Oil Corporation Limited Production de distillats désaromatisation à faible teneur en benzène pour des applications spéciales

Also Published As

Publication number Publication date
AU2001251660B2 (en) 2005-04-14
NO20025048D0 (no) 2002-10-21
EP1297100A4 (fr) 2011-04-20
NO20025048L (no) 2002-12-19
WO2001081511A3 (fr) 2002-02-21
CA2405087A1 (fr) 2001-11-01
AU5166001A (en) 2001-11-07
JP2004511579A (ja) 2004-04-15
EP1297100A2 (fr) 2003-04-02

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