Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G71/00—Treatment by methods not otherwise provided for of hydrocarbon oils or fatty oils for lubricating purposes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S208/00—Mineral oils: processes and products
  • Y10S208/02—Molecular sieve

Definitions

• the preferred faujasite contains an alkaline earth metal, particularly magnesium and the preferred hydrogenating metal is 0.01-% wt. of Pt group metal.
• the conversion may be from 40*95% wt., particularly 60-95% wt.
• the NH and H S may be produced from the feedstock in situ or preferably by a preliminary denitrogenation and desulphurization with the total effluent passing to the hydrocracking zone.
• This invention relates to the production of lubricating oils by hydrocatalytic treatment.
• the solvent extraction step can be replaced by a. hydrocatalytic treatment step using a catalyst of one or more hydrogenating metals on a refractory oxide support.
• the hydrocracking of petroleum fractions including those boiling in the lubricating oil boiling range, over catalysts of a hydrogenating metal on a zeolite support is also known.
• the main product is gasoline of reasonable quality with less middle distillate. With this product pattern, the main emphasis has been on maximum conversion to gasoline.
• a process for the production of lubricating oil and gasoline by hydrocracking comprises contacting a petroleum feedstock containing a major proportion of material boiling above 350 C. at a temperature of 350 to 450 C., a pressure of 70 to 265 bars gauge, in the presence of hydrogen, and in the presence of ammonia and hydrogen sulphide, with a catalyst comprising a hydrogenating metal and an alkali metal deficient zeolite of the faujasite type and recovering a product boiling above 350 C. having an improved viscosity index and also a gasoline product boiling below 204 C.
• the feedstock to the process is preferably a vacuum distillate boiling within the range 350-600 C. It may contain a minor proportion, preferably 5 to 30% wt., of catalytic cracker cycle oil. Since lubricating oils are marketed in several grades with relatively narrow boiling ranges, distillation to give relatively narrow boiling range cuts is required at some stage. In the present invention, a wide boiling range cut may be used as feedstock and distillation into narrower cuts given after hydrocatalytic treatment or distillation may take place before the hydrocatalytic treatment and individual cuts may be hydro treated. The former route has the advantage of avoiding blocked operation but the latter route has the advantage that optimum hydrotreating conditions may be chosen for each cut. If a vacuum residue fraction is used it should be deasphalted in the normal way.
• the preferred temperature is 380 to 420 C. and the preferred pressure to 138 bars gauge.
• Other process conditions for the hydrocatalytic treatment over the zeolite catalyst may be chosen from the following ranges:
• Suitable catalysts for the preliminary denitrogenation and desulphurization step may comprise one or more hydrogenating metals on compounds thereof chosen from Groups VIa and VIII of the Periodic Table on a acidic refractory oxide support.
• Suitable metals may be molybdenum together with one or more iron group metals, preferably from 5 to 40% of molybdenum, calculated as the trioxide M and from 1 to 15% of iron group metals, calculated as the divalent oxides (e.g. C00 or NiO).
• the acidic support may be a known catalytic cracking catalyst, for example catalysts of 50-95% wt. of silica and -50% wt. of alumina, or a support with more than 50% wt.
• alumina alumina and less than 50% wt. of an acidic oxide chosen from oxides of elements of Groups II and III and IV of the Periodic Table for example boria, silica, titania or zirconia.
• suitable catalysts may be chosen from the following ranges of composition.
• conversion in the zeolite hydrocracking process must be less than 100% wt. and is preferably from 40-95% wt. more particularly 60-95% wt. conversion to products boiling below 350 C. Thus from 5 to 60% wt. more particularly 5 to 40% wt., is recovered as product boiling above 350 C. The whole of this product boiling above 350 C.
• the present invention is thus particularly useful for use in a known hydrocracking system having three steps.
• the product from step (2) is distilled to separate the product into high and low boiling fractions with a cut point in the range 350-450 C. and at least part of the high boiling product is withdrawn as lubricating oil basestock.
• the zeolite has to be deficient in alkali metal and preferably there is an alkali metal cation deficiency of at least 50% of the theoretical alkalimetal content, and more particularly at least 75%.
• a practical upper limit is 95% wt.
• the present invention is particularly suitable for use with a faujasite catalyst containing a significant amount of an alkaline earth metal.
• alkaline earth metal includes magnesium, which is the preferred metal, the other metals being calcium strontium and barium.
• the faujasite has from 20-80% wt. of its theoretical alkali metal content replaced by alkaline earth metal cations, this corresponding, in the case of the preferred magnesium faujasite to a magnesium content of 0.9 to 3.8% wt. At least a part of the remaining cations are preferably hydrogen ions, the alkali metal content, being, preferably, 5-20%, i.e. from 0.5-2.0% wt. in the case of sodium.
• the hydrogenating metal on the zeolite is desirably a metal from Group VI or VIII of the Periodic Table, particularly the latter.
• a metal from Group VI or VIII of the Periodic Table particularly the latter.
• it is platinum group metal, particularly platinum itself or palladium.
• the metal is preferably added by ion-exchange and may be present in an amount of 0.01 to 5% wt., more particularly 0.1 to 2% wt. If present in ion exchanged from the amount of the metal should not be such as to take up all the alkali metal cation deficiency.
• NH and H S has the effect in reducing catalyst activity, though they are not permanent poisons. Consequently process conditions have to be more severe to obtain a given level of conversion when operating in the presence of NH and H S and it is this fact which is believed to provide the key to the present invention.
• a palladium-magnesium-zeolite Y catalyst gave about 50% conversion to products boiling below 371 C. at 360 C. when used in the absence of NH;, and H 8 and only increased the viscosity index of the lubricating oil fraction from 87 to 90.
• the temperature had to be increased to 390 C. to obtain a similar conversion and the viscosity index of the product increased to over 100.
• the lubricating oil product can be worked up into finished lubricating oil in known manner, e.g. it can be dewaxed and finished with bauxite or clay or by a hydrofinishing treatment. Dewaxing of the feedstock prior to the hydrocracking can be practiced but it is not preferred. Starting with wax distillate fractions boiling in the range 350 600 C. and having viscosity indices (after dewax ing) of 50-80, finished lubricating oil products with viscosity indices of -125 (as determined by the extended method) can be produced.
• the gasoline produced is rich in iso-parafiins and naphthenes and may have a research octane number clear of the order of 85.
• the amount of middle distillate boiling in the range 200 to 350 C. may be from to 30% Wt. of total product, the ratio of 15-200 C.
• gasoline EXAMPLE The feedstocks were an Egyptian wax distillate and an Egyptian distillate with 15% wt. of heavy catalytic cracker 6 Hydrogen gas rate, m. /m.
• Feed Step 1 Step 2 Feed Step 1 Step 2 Kinematic viscosity at 100 F., est 39. 69 33. 40 64 47. 27 38. 17 Kinematic viscosity at 210 F., est- 6. 29 5. 65 5. 52 7. 32 6. 32 5. 95 Viscosity index 58 102 113 58 87 109 Pour point, 0
• Each feedstock was desulphurized and denitrogenated over a nickel-molybdenum-siiica-alumina catalyst with the following inspection data.
• the total products from the desulphurization/denitrogenation stage including the NH and H 8 produced were each passed over a catalyst of palladium-magnesiumzeolite Y having the following composition.
• the viscosity indexes were determined by the extended method (ASTM Test D2270).
• the dewaxed products were obtained by dewaxing with methylisobutyl-ketone at 18 C.
• the table shows that the desulphurization/denitrogenation step 1 gave, as would have been expected, an increase in VI. It also shows that the zeolite hydrocracking step 2 gave a further improvement in VI and that this further VI improvement was obtained with only a moderate further decrease in viscosity. The table also shows that the feedstock containing the cycle oil gave the higher VI products.
• a process for the production of lubricating oil and gasoline by hydrocracking comprising contacting a petroleum feedstock containing a major proportion of material boiling above 350 C. and containing from 0.02 to 0.30% Wt. of nitrogen and 0.2 to 3.0% wt. of sulphur at a temperature of 350 to 450 C., a pressure of 70 to 265 bars gauge, a space velocity of 0.5 to 5 v./v./hr., a hydrogen gas rate of 562 to 2240 m. /m. and in the presence of ammonia and hydrogen sulphide with a catalyst comprising from 0.01 to 5% wt.
• a process as claimed in claim 1 wherein the conversion to products boiling below 350 C. is from 60 to 90% wt.
• OaA1 O .37 SiO should read Na O-zAl O z3-7SiO line 44 "from” should read form Column 6 line 4, "NH” should read NH: lines 11 and 12, "convrsion” should read conversion --4.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

Applications Claiming Priority (1)

Publications (1)

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ID=10097411

Family Applications (1)

Country Status (9)

Cited By (5)

Families Citing this family (4)

• 1972
  • 1972-04-17 GB GB1756572A patent/GB1400013A/en not_active Expired
• 1973
  • 1973-04-02 US US00346855A patent/US3804742A/en not_active Expired - Lifetime
  • 1973-04-03 NL NL7304605A patent/NL7304605A/xx not_active Application Discontinuation
  • 1973-04-10 JP JP48040776A patent/JPS4918102A/ja active Pending
  • 1973-04-13 FR FR7313497A patent/FR2180796B1/fr not_active Expired
  • 1973-04-13 IT IT49439/73A patent/IT980211B/it active
  • 1973-04-14 DE DE2318888A patent/DE2318888A1/de active Pending
  • 1973-04-17 CA CA169,480A patent/CA978124A/en not_active Expired
  • 1973-04-17 BE BE130127A patent/BE798349A/xx unknown

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