EP0226289B1 - Traitement d'un gazole sous vide aromatique en vue de la production d'un carburéacteur - Google Patents

Traitement d'un gazole sous vide aromatique en vue de la production d'un carburéacteur Download PDF

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Publication number
EP0226289B1
EP0226289B1 EP86307809A EP86307809A EP0226289B1 EP 0226289 B1 EP0226289 B1 EP 0226289B1 EP 86307809 A EP86307809 A EP 86307809A EP 86307809 A EP86307809 A EP 86307809A EP 0226289 B1 EP0226289 B1 EP 0226289B1
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Prior art keywords
jet fuel
gas oil
feed
vacuum gas
aromatics
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EP86307809A
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German (de)
English (en)
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EP0226289A3 (en
EP0226289A2 (fr
Inventor
Kenneth Michael Mitchell
Stuart Shan-San Shih
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Priority to AT86307809T priority Critical patent/ATE72266T1/de
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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
    • 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
    • C10G65/043—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 change in the structural skeleton

Definitions

  • This invention relates to the production of premium jet fuel from aromatic vacuum gas oil.
  • jet fuel Refining petroleum crude oils to obtain jet fuel is well known.
  • the jet fuel must meet certain specifications for freeze point, pour point, smoke point and weight percent sulfur. It may be necessary to subject these fuels to additional processing to meet required specifications.
  • U. S. Patent No. 4,501,926 to LaPierre et al gas oil and H2 contact zeolite beta catalyst to selectively isomerize the paraffinic waxy components in a gas oil feed.
  • U. S. Patent No. 4,501,926 discloses other useful feedstocks, including crude oils, kerosenes, jet fuels, lubricating oil stocks, heating oils and other distillate fractions, whose pour point and viscosity need to be maintained within certain specification limits.
  • U. S. Patent No. 3,573,198 to Parker et al teaches smoke point improvement of jet fuel kerosene fractions by treating a sulfurous kerosene fraction by a two-stage process.
  • the first stage principally desulfurizes and the second stage principally saturates aromatics by contact with a catalyst of alumina, a halogen component, a Group VIII noble metal component and a Group VII-B metallic component.
  • U. S. 3,573,198 does not suggest upstream processing most appropriate for combination with its process. Highly olefinic/aromatic kerosene is the least desirable feed for this process.
  • U. S. Patent No. 4,427,534 to Brunn et al discloses production of jet and diesel fuels from highly aromatic oils using a sulfided, halogen-promoted Group VIB-Group VIII metal on an alumina-containing support.
  • the process has the disadvantage that it employs hydrocracking, which opens aromatic molecules to form paraffinic material. By opening aromatic rings, the hydrocracked products can have a higher pour point than the feed to hydrocracking.
  • the present invention provides a process for producing jet fuel from a vacuum gas oil feed having at least 20 to 50 wt % aromatics and boiling above 343°C (650°F) by contacting the feed with a dewaxing catalyst comprising a hydrogenation component and zeolite beta having a silica:alumina ratio of at least 30:1 at 199-538°C (390° to 1000°F), a pressure of atmospheric to 10,400 kPa (1500 psig), a liquid hourly space velocity of 0.2 to 5.0 hr ⁇ 1, in the presence of hydrogen to produce a dewaxed effluent stream, wherein most aromatics in the feed are unchanged; separating the dewaxed effluent stream into a kerosene fraction containing hydrocarbons boiling below 343°C (650°F) and a heavier fraction; hydrotreating the kerosene fraction with a conventional hydrotreating catalyst under conventional hydrotreating conditions to produce a hydrotreated kerosene stream; and recovering from the hydro
  • the process of the present invention produces jet fuel having a low freeze point and low pour point from a vacuum gas oil boiling above 288°C (550°F) preferably above 343°C (650°F).
  • Vacuum gas oils typically boil in the range from 288 to 566°C (550° to 1050°F), more usually 343 to 454°C (650° to 850°F).
  • the process of the present invention produces jet fuel from highly aromatic (at least 20-50 wt % aromatics) feeds with minimal conversion of aromatics during isomerization of paraffins into jet fuel hydrocarbons, thus improving jet fuel quality by not converting the aromatics into higher pour point paraffins.
  • the process also improves jet fuel quality by mild hydrotreating of the kerosene cut separated from other hydrocarbons in the effluent from isomerization, thus allowing easy processing to produce a jet fuel which meets jet fuel specifications for aromatics content, pour point, freeze point, sulfur content and smoke point.
  • the figure illustrates isomerization dewaxing followed by hydrotreating of a kerosene fraction.
  • the vacuum gas oil feed comprises aromatics, paraffinic, waxy components and sulfur compounds.
  • the vacuum gas oil stream 12 is combined with a hydrogen stream 14 to form a combined stream 16.
  • the vacuum gas oil comes from a vacuum distillation tower (not shown).
  • the combined stream 16 passes into reactor 20, preferably a co-current downflow trickle bed reactor. Feed contacts catalyst comprising a hydrogenation component and zeolite beta to produce a dewaxed effluent stream 22.
  • the aromatics are substantially unchanged in the dewaxing unit 20.
  • the preferred isomerization conditions are a temperature of 199 to 538°C (390° to 1000°F), a pressure of atmospheric to 10,400 kPa (1500 psig), a liquid hourly space velocity (LHSV) from 0.2 to 5.0 hr ⁇ 1 and a hydrogen feed rate of 90 to 900, n l/l, normal liters per liter of liquid feed (500 to 5000 SCF/bbl of vacuum gas oil).
  • the temperature is 371 to 454°C (700° to 850°F)
  • the pressure is 2200 to 3500 kpa (300 to 500 psig)
  • the liquid hourly space velocity is 0.5 to 2.0 hr ⁇ 1
  • the hydrogen feed rate is 180 to 540 n l/l (1000 to 3000 SCF/bbl).
  • the dewaxed effluent is separated by separator 30 into a vapor stream 34 and a liquid stream 36.
  • the vapor H2 and C1-C4 hydrocarbons
  • the liquid comprising C5+ hydrocarbons, enters distillation tower 40 which produces a naphtha stream 42, typically C5 to 143°C (290°F) a kerosene stream 46 and a bottoms stream 44.
  • the aromatics impair the subsequent hydrotreating of the kerosene.
  • Tower 40 facilitates downstream hydrotreating of the kerosene because the aromatics (which are not changed much in reactor 20) are still high boiling and concentrate in the bottoms stream 44.
  • the kerosene stream 46 is combined with hydrogen from stream 48 to form a hydrotreater feed stream 49, which enters hydrotreater 50.
  • the kerosene 46 has some olefins and sulfur compounds.
  • the hydrotreater 50 removes some of the sulfur and saturates some of the olefins.
  • Hydrotreater 50 contains conventional hydrotreating catalysts, and operates at conventional conditions.
  • the hydrotreater operates at 1800 to 5600 kPa (250 to 800 psig), a temperature of 240 to 427°C (400° to 800°F), a liquid hourly space velocity from 0.5 to 10.0 hr ⁇ 1, and a hydrogen feed rate of 90 to 900 n l/l (500 to 5000 SCF/bbl).
  • the hydrotreated effluent stream 52 passes from hydrotreater 50 into separator 60 which separates stream 52 into a C4- vapor stream 64 and a C5+ liquid stream 66.
  • the liquid stream 66 passes to a stripper 70.
  • the hydrotreated liquid is preferably steam-stripped by steam, from line 72 into a naphtha stream 74 and a jet fuel stream 76.
  • the jet fuel stream 76 typically comprises 143 to 288°C (290° to 550°F) hydrocarbons.
  • the jet fuel stream 76 has a smoke point within 1 mm of the smoke point of the kerosene stream 46.
  • the jet fuel, stream 76 preferably meets jet fuel smoke point specifications, and may be blended into the refinery jet fuel pool.
  • Boiling point of the jet fuel is related to freeze point.
  • the higher boiling point components have higher freeze points than the lower boiling point components.
  • Distillation cut points can be adjusted by conventional means, e.g., by changing fractionator reflux rates, temperatures, etc.
  • the freeze point may range from -40° to -50°C (-40° to -58°F).
  • the isomerization dewaxing catalyst comprises zeolite beta with a hydrogenation component.
  • Zeolite beta is described in U.S. Patent Nos. 3,308,069 and Re. 28,341.
  • the hydrotreating catalyst and process are conventional.
  • the hydrotreating catalyst is Ni, Mo, Co, W, NiMo, CoMo, etc., on an amorphous support such as alumina.
  • Dewaxing and hydrotreating were run in a 100 cc downflow fixed bed test reactor.
  • the test reactor had a 2.5 cm (1-inch nominal) inside diameter and a 91 cm (36-inch) length, including a 30 cm (12-inch) preheater, a 30 cm (12-inch) catalyst space and a 30 cm (12-inch) bottoms space.
  • 75 cc of catalyst was used.
  • H2 was added at a rate of 360 nl/l (2000 SCF/bbl).
  • Examples 1-5 illustrate prior art processes (Examples 1-4) or processes which do not form part of the state of the art but which are not claimed as the invention (Example 5).
  • the 204-371°C (400-700°F) fraction is a typical light gas oil.
  • the 343-454°C (650-850°F) fraction is a typical aromatic vacuum gas oil, and is preferred feedstock for use in the present invention.
  • This example reports catalyst properties of two hydrotreating catalysts and one isomerization dewaxing catalyst.
  • the isomerization dewaxing catalyst, platinum zeolite beta comprised about 35 wt % alumina 65 wt % zeolite beta to which was added 0.56 wt % platinum.
  • the catalyst was prepared by blending 65 wt % zeolite beta and 35 wt % alumina with water. This was then extruded to 1.6m (1/16") outside diameter pellets and dried at 121°C (250°F) in nitrogen. Then, the catalyst was heated at 2.8°C/min (5°F/min) in nitrogen and calcined in nitrogen for 3 hours at 538°C (1000°F) then calcined in air for 3 hours at 538°C (1000°F).
  • the air-calcined catalyst was steamed 10 hours at 538°C (1000°F) and 1 atm steam pressure.
  • the catalyst was ammonium-exchanged twice at room temperature with 1 normal NH4NO3, washed with water and dried at 121°C (250°F) overnight. Then, the catalyst was exchanged for 12 hours at room temperature with Pt(NH3)4Cl2, at a concentration of 4 milliliters water per gram of platinum salt, with stirring. The catalyst was then washed 4 times until free of chlorine.
  • the washed catalyst was then dried at 121°C (250°F) overnight and calcined for 3 hours at 349°C (660°F) in a 60% air, 40% N2 mixture which has a dew point of -6°C (22°F).
  • the resulting zeolite beta catalyst had an alpha value of 50 based on zeolite.
  • the significance of the alpha value and a method for determining it are described in U. S. Patent No. 4,016,218 and J. Catalysis , 61, 390 etseq (1980).
  • Catalysts having an alpha value based on zeolite of 10 to 150, preferably 10 to 100, or most preferably 30 to 70, are preferred for isomerization dewaxing.
  • Alpha can be changed by steaming, by alkali-exchange or by varying the silica:alumina ratio of the zeolite.
  • the reactor pressure was 2500 kPa (350 psig), the liquid hourly space velocity was 1.0 hr ⁇ 1, the temperature was 416 to 421°C (780° to 790°F), with 356 nl/l (2000 SCF/bbl) of H2.
  • the reactor effluent was distilled to produce a 143 to 288°C (290° to 550°F) fraction, equivalent to stream 46 of the figure.
  • Table 4 lists the properties of the 143°C+ (290°F+) effluent and its 143 to 288°C (290° to 550°F) fraction.
  • the 143 to 288°C (290° to 550°F) fraction meets smoke point requirements, but has too much sulfur (0.67 wt %) and olefins (7.7 vol %).
  • This example demonstrates isomerization-dewaxing followed by hydrotreating of the entire effluent.
  • the entire 143°C+ (290°F+) effluent from the test reactor is hydrotreated using the conventional NiMo/Al2O3 hydrotreating catalyst listed in Table 2.
  • the effluent from hydrotreater was distilled to form a jet fuel fraction 143 to 288°C (290° to 550°F) whose properties are summarized in Table 5.
  • Hydrotreating the entire 143°C (290°F+) dewaxing reactor effluent degraded the jet fuel as shown by its lower smoke point and higher aromatics content compared to the unhydrotreated 143-288°C (290° to 550°F) fraction produced in Example 4 and listed in Table 4.
  • This example demonstrates isomerization-dewaxing of a vacuum gas oil followed by hydrotreating the kerosene fraction of the dewaxed effluent.
  • the dewaxed effluent of Example 4 is fractionated to produce a kerosene fraction of 143 to 288°C (290° to 550°F) representing stream 46 of the figure.
  • This fraction was hydrotreated at varying temperatures using the conventional (NiMo/Al2O3) hydrotreating catalyst of Table 2.
  • the hydrotreated material was stripped to recover a jet fuel product of 143 to 288°C (290° to 550°F). Hydrotreating conditions and jet fuel product properties are listed in Table 5.
  • Example 5 the entire 143°C+ (290°F+) isomerization dewaxing reactor effluent is hydrotreated. Even though the boiling range of the jet fuel product is the same (because of fractionation to obtain a 143 to 288°C product) in Examples 5-8, the jet fuel made in Example 5 is not as good as the jet fuel made in Examples 6-8.
  • Example 6 Increasing the hydrotreating temperature from 316°C (601°F), in Example 6 to 344°C (to 651°F) in Example 7 gave a jet fuel product having less sulfur and a higher smoke point.
  • Example 8 Hydrotreating at 371°C (700°F), in Example 8, gives a jet fuel product with an 18.5 mm smoke point, as opposed to the 20.0 mm smoke point of the product from Example 7.
  • the results in Table 5 indicate that hydrotreating the jet fuel fraction, the 143-288°C (290° to 550°F) fraction, separately from 288°C (550°F+) components, improves the jet fuel quality, as shown by a higher diesel index, higher smoke point and lower volume percent olefins.
  • the 143-288°C (290° to 550°F) fractions after hydrotreating, as shown in Examples 6-8, can be blended directly into refinery jet fuel pools.
  • the present invention provides jet fuel which meets typical freeze point, pour point and smoke point specifications.
  • the process of the present invention can produce jet fuel from 343°C+ (650°F+) feedstocks which are highly aromatic.
  • the process selectively cracks heavy paraffins to jet fuel boiling range materials while it converts little of the heavy aromatics in the feed into the jet fuel fraction.
  • Jet fuel quality is improved by mildly hydrotreating the kerosene cut separately from heavier hydrocarbons.
  • the present invention also removes aromatics from the hydrotreater feedstock by fractionating heavier hydrocarbons away from the kerosene fraction prior to hydrotreating, because aromatics tend to concentrate in the heavier hydrocarbons.
  • Isomerization-dewaxing followed by fractionating and hydrotreating, produces high quality jet fuel at low pressures even from chargestocks containing 20 to 50+ wt. % aromatics. This is significant since refineries will process more heavy crudes which contain more aromatics.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Claims (7)

  1. Un procédé de production d'un carburant pour réacteur à partir d'une charge de gazole renfermant au moins 20 à 50% d'aromatiques et dont le point d'ébullition est supérieur à 343°C (650°F) par mise au contact de la charge avec un catalyseur de déparaffinage comprenant un composant d'hydrogénation et une zéolite bêta dont le rapport silice/alumine est au moins égal à 30/1 à 199 à 538°C (390° à 1000°F), sous une pression comprise entre la pression atmosphérique et 10 400 kPa (1500 psig), avec une vitesse spatiale horaire liquide de 0,2 à 5,0 h⁻¹, en présence d'hydrogène pour obtenir un courant d'effluent déparaffiné dans lequel la plupart des aromatiques de la charge restent inchangés, caractérisé en ce que le courant d'effluent déparaffiné est tout d'abord séparé en une fraction de kérosène contenant des hydrocarbures dont le point d'ébullition est inférieur à 340°C (650°F) et en une fraction plus lourde, et en ce que la fraction kérosène est ensuite soumise à un hydrotraitement en présence d'un catalyseur classique d'hydrotraitement dans des conditions classiques d'hydrotraitement pour produire un courant de kérosène hydrotraité qui est récupéré en tant que carburant pour réacteur.
  2. Le procédé selon la revendication 1, caractérisé en outre en ce que le point d'ébullition de la fraction kérosène est compris entre 143° et 288°C (290° et 550°F).
  3. Le procédé selon la revendication 1 ou 2, caractérisé en outre en ce que le déparaffinage est mis en oeuvre sous une pression de 2200 à 3500 kPa (300 à 500 psig).
  4. Le procédé selon l'une quelconque des revendications précédentes, caractérisé en outre en ce que le composant d'hydrogénation du catalyseur de déparaffinage comprend de 0,1 à 5,0% en poids d'un métal noble du groupe VIII de la classification périodique des éléments.
  5. Le procédé selon la revendication 4, caractérisé en outre en ce que le composant d'hydrogénation renferme de 0,1 à 1,2% en poids de platine.
  6. Le procédé selon l'une quelconque des revendications précédentes, caractérisé en outre en ce que le point d'ébullition de la charge de gazole de distillation sous vide est supérieur à 343°C (650°F) et que cette charge contient, en pourcentage pondéral, plus d'aromatiques que de paraffines.
  7. Le procédé selon l'une quelconque des revendications précédentes, caractérisé en outre en ce que le gazole de distillation sous vide contient au moins 2,0% en poids de soufre, l'étape de déparaffinage convertit une portion de la charge en oléfines, la fraction kérosène comprend des oléfines et du soufre, et le traitement classique d'hydrotraitement élimine une partie du soufre, et conduit à la saturation d'une majorité des oléfines dans la fraction kérosène.
EP86307809A 1985-10-15 1986-10-09 Traitement d'un gazole sous vide aromatique en vue de la production d'un carburéacteur Expired - Lifetime EP0226289B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86307809T ATE72266T1 (de) 1985-10-15 1986-10-09 Bearbeitung von aromatischem vakuumgasoel zur herstellung von duesentreibstoff.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78760085A 1985-10-15 1985-10-15
US787600 1985-10-15

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EP0226289A2 EP0226289A2 (fr) 1987-06-24
EP0226289A3 EP0226289A3 (en) 1988-08-31
EP0226289B1 true EP0226289B1 (fr) 1992-01-29

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EP86307809A Expired - Lifetime EP0226289B1 (fr) 1985-10-15 1986-10-09 Traitement d'un gazole sous vide aromatique en vue de la production d'un carburéacteur

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EP (1) EP0226289B1 (fr)
JP (1) JPS6295388A (fr)
AT (1) ATE72266T1 (fr)
AU (1) AU592372B2 (fr)
BR (1) BR8605035A (fr)
CA (1) CA1274205A (fr)
DE (1) DE3683740D1 (fr)
ZA (1) ZA867651B (fr)

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JP2013185493A (ja) * 2012-03-08 2013-09-19 Mitsubishi Heavy Ind Ltd 燃料供給システム、スクラムジェットエンジン及びその動作方法
JP6021661B2 (ja) 2013-01-30 2016-11-09 三菱重工業株式会社 燃料供給システム、スクラムジェットエンジン及びその動作方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419220A (en) * 1982-05-18 1983-12-06 Mobil Oil Corporation Catalytic dewaxing process
JPS5924791A (ja) * 1982-07-31 1984-02-08 Toa Nenryo Kogyo Kk 低流動点石油製品の製造方法
US4601993A (en) * 1984-05-25 1986-07-22 Mobil Oil Corporation Catalyst composition dewaxing of lubricating oils

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Publication number Publication date
EP0226289A3 (en) 1988-08-31
CA1274205A (fr) 1990-09-18
EP0226289A2 (fr) 1987-06-24
DE3683740D1 (de) 1992-03-12
BR8605035A (pt) 1987-07-14
ATE72266T1 (de) 1992-02-15
ZA867651B (en) 1988-05-25
AU592372B2 (en) 1990-01-11
JPS6295388A (ja) 1987-05-01
AU6308086A (en) 1987-04-16

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