EP1297099A2 - Low sulfur distillate fuels - Google Patents
Low sulfur distillate fuelsInfo
- Publication number
- EP1297099A2 EP1297099A2 EP01925061A EP01925061A EP1297099A2 EP 1297099 A2 EP1297099 A2 EP 1297099A2 EP 01925061 A EP01925061 A EP 01925061A EP 01925061 A EP01925061 A EP 01925061A EP 1297099 A2 EP1297099 A2 EP 1297099A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- fuel composition
- wppm
- distillate fuel
- sulfur level
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 118
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 238000009835 boiling Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 4
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- 230000006835 compression Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000007789 gas Substances 0.000 description 46
- 238000004128 high performance liquid chromatography Methods 0.000 description 43
- 229910052739 hydrogen Inorganic materials 0.000 description 41
- 239000001257 hydrogen Substances 0.000 description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 38
- 239000003054 catalyst Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 27
- 239000002283 diesel fuel Substances 0.000 description 17
- 238000004949 mass spectrometry Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000013618 particulate matter Substances 0.000 description 8
- 239000012808 vapor phase Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000004808 supercritical fluid chromatography Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 101100116283 Arabidopsis thaliana DD11 gene Proteins 0.000 description 1
- 101100192207 Arabidopsis thaliana PTAC10 gene Proteins 0.000 description 1
- 101100310953 Arabidopsis thaliana SRD2 gene Proteins 0.000 description 1
- 101100096598 Caenorhabditis elegans srd-3 gene Proteins 0.000 description 1
- 101100096611 Caenorhabditis elegans srd-7 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101100001085 Dictyostelium discoideum ado-2 gene Proteins 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101100269674 Mus musculus Alyref2 gene Proteins 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 102220486681 Putative uncharacterized protein PRO1854_S10A_mutation Human genes 0.000 description 1
- 102220470087 Ribonucleoside-diphosphate reductase subunit M2_S20A_mutation Human genes 0.000 description 1
- 101100388638 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) ECM23 gene Proteins 0.000 description 1
- 101100310949 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SRD1 gene Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 102220000832 rs119103279 Human genes 0.000 description 1
- 102220065736 rs543286136 Human genes 0.000 description 1
- 102220059022 rs786201869 Human genes 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a distillate fuel composition boiling in the range of about 190°C to 400°C with a T10 point greater than 205°C, and having a sulfur level of less than about 100 wppm, a total aromatics content of about 15 to 35 wt.%, a polynuclear aromatics content of less than about 3 wt.%, wherein the ratio of total aromatics to polynuclear aromatics is greater than about 11.
- 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
- unb ⁇ rned 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
- 10-23.9 wt.% total aromatics is disclosed.
- further advances in sulfur-sensitive after-treatment technology have led to increasing demand for lower levels of sulfur in diesel fuels.
- 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 their patent.
- a distillate fuel composition boiling in the range of about 190°C to 400°C with a T10 point greater than 205°C, and having a sulfur level of less than about 100 wppm, a total aromatics content of about 15 to 35 wt.%, a polynuclear aromatics content of less than about 3 wt.%, wherein the ratio of total aromatics to polynuclear aromatics is greater than about 11.
- the sulfur level is less than about 50 wppm.
- the total aromatics content is from about 20 to 35 wt.%.
- the ratio of total aromatics to polynuclear aromatics is at least 15.
- the invention is a fuel composition comprising:
- the fuel is employed in a compression ignition (e.g.,
- Figure 1 hereof shows one preferred process scheme used to prepare distillate fuel compositions of present invention.
- This process scheme includes two co-current hydrodesulfurization stages with once through hydrogen-containing treat gas in the second hydrodesulfurization stage.
- Figure 2 hereof shows a plot that defines the composition of distillate products of the present invention where the sulfur content is less than 100 ppm and the ratio of total aromatics to polynuclear aromatics is greater than about 11.
- Feedstreams suitable for producing the low emissions distillate fuel compositions of this invention are those petroleum based feedstreams boiling in the distillate range and above. Such feedstreams typically have a boiling range from about 190 to about 400°C, preferably from about 200 to about 370°C. These feedstreams typically contain greater than about 3,000 wppm sulfur. Non-limiting examples of such feedstreams include virgin distillates, light cat cycle oils, light coker oils, etc. It is highly desirable for the refiner to upgrade these types of feedstreams by removing as much of the sulfur as possible, as well as to saturate aromatic compounds.
- FIG. 1 It is not critical how the distillate fuel compositions are produced.
- One preferred process for producing the fuel products of the present invention is illustrated in Figure 1 hereof.
- the preferred process uses once-through hydrogen treat gas in a second hydrodesulfurization stage and optionally in a first hydrodesulfurization stage as well. Relatively low amounts of hydrogen are utilized in the second hydrodesulfurization stage in such a way that very low levels of sulfur in the liquid product can be achieved while minimizing the amount of hydrogen consumed via saturation of the aromatics.
- the first hydrodesulfurization stage will reduce the levels of both sulfur and nitrogen, with sulfur levels being less than about 1,000 wppm, preferably less than about 500 wppm.
- the second hydrodesulfurization stage will reduce sulfur levels to less than about 100 wppm, preferably to less than about 50 wppm.
- 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 this reaction stage can contain only one reaction zone 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 18, which treat gas will typically be from another refinery process unit, such as a naphtha hydrofiner.
- treat gas can also be recycled via lines 20, 22, and 16 from separation zone SI .
- 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 feedstock 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 of 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 passes 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 which may be cascaded or otherwise obtained from a refinery process unit such as a naphtha hydrofiner.
- a refinery process unit such as a naphtha hydrofiner.
- the treat gas can be introduced into the bottom section of reactor R2 and flowed countercurrent to the downward flowing liquid feedstream. It is preferred that 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 stage, more preferably less than about 2 times, and most preferably less than about 1.5 times.
- the feedstream and hydrogen-containing treat gas pass, preferably cocurrently, 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 100 wppm sulfur, preferably less than about 50 wppm sulfur, and more preferably less than 10 wppm sulfur.
- Suitable hydrodesulfurization catalysts for use in the reaction vessel R2 in the present invention include conventional hydrodesulfurization catalyst, such as those previously described for use in Rl .
- Noble metal catalysts may also be employed, preferably the noble metal is 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.
- second reaction stage R2 can be run in two or more temperature zones and in either cocurrent or countercurrent mode.
- two or more temperature zones we mean that reaction stage R2 will contain two or more separate beds of catalyst wherein at least one such bed is operated at a temperature of at least 25°C lower than the other catalyst beds comprising the reaction stage.
- the lower temperature zone(s) be operated at a temperature of at least about 50°C lower than the higher temperature zone(s).
- the lower temperature zone be the last downstream zone(s) with respect to the flow of feedstock.
- the second reaction stage be operated in either co-current or countercurrent mode.
- countercurrent mode we mean that the treat gas will flow upwardly, counter to the downflowing feedstock.
- the reaction product from second hydrodesulfurization stage R2 is passed via line 35 to a second separation zone S2 wherein a vapor product, containing hydrogen, is preferably recovered overhead via line 32 and may be removed from the process via line 36.
- a vapor product containing hydrogen
- the treat gas is referred to as a "once-through" treat gas.
- all or a portion of the vapor product may be cascaded to hydrodesulfurization stage Rl via lines 34 and 16.
- cascaded when used in conjunction with treat gas is meant to indicate a stream of hydrogen- containing treat gas separated as a vapor effluent from one stage that is sent to the inlet of a reaction stage without passing through a gas compressor. That is, the treat gas flows from a downstream reaction 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.
- Figure 1 also shows several optional process schemes.
- line 38 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.
- typical hydroprocessing temperatures will range from about 200°C to about 400°C at pressures from about 50 psig to about 3,000 psig, preferably 50 to 2,500 psig, and more preferably about 150 to 1,500 psig.
- reaction stage R2 can be operated in two or more temperature zones wherein the most downstream temperature zone is at least about 25°C , preferably about 35°C, cooler than the upstream temperature zone(s).
- 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.
- all or a portion of the hydrogen required for the first stage hydroprocessing be 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.
- 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.
- 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).
- Such distillate fuels have moderate levels of total aromatics, reducing the cost of producing cleaner-burning diesel fuel and also reducing C0 2 emissions by minimizing the amount of hydrogen consumed in the process.
- the preferred 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 may be 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.
- the distillate compositions of the present invention contain less than about 100 wppm, preferably less than about 50 wppm, more preferably less than about 10 wppm sulfur. They will also have a total aromatics content from about 15 to 35 wt.%, preferably from about 20 to 35 wt.%, and most preferably from about 25 to 35 wt.%.
- the PNA content of the distillate product compositions obtained by the practice of the present invention will be less than about 3 wt.%), preferably less than about 2 wt.%, and more preferably less than about 1 wt.%.
- the aromatics to PNA ratio will be at least about 11, preferably at least about 13, and more preferably at least about 15.
- the distillate fuels of the present invention have relatively low amounts of low boiling material with a T10 distillation point of at least about 205°C.
- the aromatics to PNA ratio will be at least about 11, preferably at least about 13, and more preferably at least about 15. 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 C0 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.
- 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/ A1 2 0 3 (Akzo-Nobel KF842/840) and CoMo/Al 2 0 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.
- the liquid product stream from this first hydrodesulfurization stage was used as feedstream to the second hydrodesulfurization stage, which product stream is described under the feed properties heading in Table 1 below.
- the process conditions for this second hydrodesulfurization stage are also shown in the table below.
- a commercial NiMo catalyst (Criterion C-411 containing 2.6 wt.% Ni and 14.3 wt.% Mo) was used in all of the runs.
- Examples 1 - 5 in Table 1 demonstrate that products with less than 100 wppm sulfur 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 1-5 also demonstrate that products with a total aromatics content between 15 and 35 wt.% can be produced with total aromatics/PNA ratios of greater than 11.
- Comparative Examples A-F in Table 2 below are all fuel compositions containing less than 100 ppm sulfur. Comparative examples A-F describe fuels that have total aromatics levels greater than 15 wt.%. All of them have a ratio of total aromatics to PNAs less than about 10, which is outside the range of the fuel compositions of the present invention.
- FIA fluorescence indicator analysis
- MS mass spectrophotometry
- SFC supercritical fluid chromatography
- the level of the pollutants NOx and particulate matter is reduced to values which comply with current and projected levels specified in environmental legislation, i.e., NOx below 0.5g/Km and particulate matter below 0.05g/Km. These values/levels are significantly lower than that for comparable fuels in which the aromatic content split (i.e., the total aromatics to PNA ratio) falls outside the ranges of the present invention as shown in the examples below.
- Example 6 was prepared in a commercial hydrodesulfurization unit from a virgin distillate feed using a conventional CoMo/Al 2 0 3 catalyst and represents a typical commercial diesel fuel composition.
- Example 5 is a composition according to the present invention, as set forth in Table 1. 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. On the basis of the differences in fuel parameters between
- Example 6 and Example 5 the EPEFE calculations would lead one to expect lower particulate matter and NOx emissions for the fuel of Example 5.
- Example 6 The fuel of Example 6 was also compared to another fuel of the present invention, Example 7. Table 6 below shows the properties of these fuels.
- Example 7 The relative emissions levels achieved from the Example 7 fuel tests (relative to Example 6) were evaluated and compared with established EPEFE and AutoOil predictions, as in the comparison between the fuels of Examples 5 and 6.
- EPEFE+EUDC cold-start legislated European type certification drive cycle
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US553108 | 2000-04-20 | ||
US09/553,108 US6893475B1 (en) | 1998-12-08 | 2000-04-20 | Low sulfur distillate fuels |
PCT/US2001/012519 WO2001081510A2 (en) | 2000-04-20 | 2001-04-17 | Low sulfur distillate fuels |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1297099A2 true EP1297099A2 (en) | 2003-04-02 |
EP1297099A4 EP1297099A4 (en) | 2011-04-20 |
EP1297099B1 EP1297099B1 (en) | 2017-11-01 |
Family
ID=24208168
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Application Number | Title | Priority Date | Filing Date |
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EP01925061.2A Expired - Lifetime EP1297099B1 (en) | 2000-04-20 | 2001-04-17 | Low sulfur distillate fuels |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1297099B1 (en) |
JP (1) | JP4919572B2 (en) |
AU (2) | AU2001251659B2 (en) |
CA (1) | CA2404931A1 (en) |
NO (1) | NO20025019L (en) |
WO (1) | WO2001081510A2 (en) |
Families Citing this family (1)
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CN102229813B (en) * | 2011-05-23 | 2013-07-17 | 陕西超能石化科技有限公司 | Multifunctional desulphurization auxiliary agent of distillate of FCC device and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0856573A2 (en) * | 1997-01-29 | 1998-08-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Diesel fuel composition for reduced particulate emission |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
US6004361A (en) * | 1993-03-05 | 1999-12-21 | Mobil Oil Corporation | Low emissions diesel fuel |
AU669439B2 (en) * | 1993-03-05 | 1996-06-06 | Mobil Oil Corporation | Low emissions diesel fuel |
US5792339A (en) * | 1994-05-10 | 1998-08-11 | Tosco Corporation | Diesel fuel |
US5807413A (en) * | 1996-08-02 | 1998-09-15 | Exxon Research And Engineering Company | Synthetic diesel fuel with reduced particulate matter emissions |
JP3744672B2 (en) * | 1997-01-29 | 2006-02-15 | 株式会社豊田中央研究所 | Gas oil composition for reducing particulates |
WO2000020534A1 (en) * | 1998-10-05 | 2000-04-13 | Sasol Technology (Pty.) Ltd. | Biodegradable middle distillates and production thereof |
CA2350408C (en) * | 1998-11-12 | 2010-05-04 | Mobil Oil Corporation | Diesel fuel |
-
2001
- 2001-04-17 EP EP01925061.2A patent/EP1297099B1/en not_active Expired - Lifetime
- 2001-04-17 CA CA002404931A patent/CA2404931A1/en not_active Abandoned
- 2001-04-17 JP JP2001578584A patent/JP4919572B2/en not_active Expired - Fee Related
- 2001-04-17 AU AU2001251659A patent/AU2001251659B2/en not_active Ceased
- 2001-04-17 AU AU5165901A patent/AU5165901A/en active Pending
- 2001-04-17 WO PCT/US2001/012519 patent/WO2001081510A2/en active Application Filing
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2002
- 2002-10-18 NO NO20025019A patent/NO20025019L/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0856573A2 (en) * | 1997-01-29 | 1998-08-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Diesel fuel composition for reduced particulate emission |
Non-Patent Citations (1)
Title |
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See also references of WO0181510A2 * |
Also Published As
Publication number | Publication date |
---|---|
CA2404931A1 (en) | 2001-11-01 |
EP1297099A4 (en) | 2011-04-20 |
EP1297099B1 (en) | 2017-11-01 |
NO20025019D0 (en) | 2002-10-18 |
NO20025019L (en) | 2002-12-19 |
WO2001081510A3 (en) | 2002-01-24 |
JP4919572B2 (en) | 2012-04-18 |
JP2003531277A (en) | 2003-10-21 |
AU5165901A (en) | 2001-11-07 |
WO2001081510A2 (en) | 2001-11-01 |
AU2001251659B2 (en) | 2006-06-01 |
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