US3732156A - Production of lubricating oils - Google Patents

Production of lubricating oils Download PDF

Info

Publication number
US3732156A
US3732156A US00145492A US3732156DA US3732156A US 3732156 A US3732156 A US 3732156A US 00145492 A US00145492 A US 00145492A US 3732156D A US3732156D A US 3732156DA US 3732156 A US3732156 A US 3732156A
Authority
US
United States
Prior art keywords
zeolite
catalyst
boiling
product
decationised
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.)
Expired - Lifetime
Application number
US00145492A
Other languages
English (en)
Inventor
R Bennett
F Morum
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP PLC
Original Assignee
BP PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Application granted granted Critical
Publication of US3732156A publication Critical patent/US3732156A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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 hydrogenating metal is preferably a platinum group metal and the preferred conversion is 40-95% wt. of product boiling below 350 C.
  • Products, after dewaxing, of 85-125 V.I. can be produced from feedstocks of 60- 80 V.I.
  • This invention relates to the production of lubricating oils by hydrocatalytic treatment.
  • the production of lubricating oils requires the steps of solvent extraction to remove aromatics and improve viscosity index, solvent dewaxing to remove n-paraffins and improve pour point and a finishing treatment to improve colour and colour stability.
  • 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.
  • Some breakdown of the feedstock is unavoidable in this hydrocatalytic treatment and gasoline, kerosine and gas oils are also recovered.
  • These lower boiling products contain appreciable amounts of middle distillates as well as gasoline, which is of low octane number, and this type of by-product pattern is not always desirable.
  • a process for the production of lubricating oil and gasoline comprises contacting a petroleum feedstock boiling above 350 C. at a temperature of 300 to 420 C., a pressure of 6900 to 26,700 kN./m. g. and in the presence of hydrogen with a catalyst comprising a hydrogcnating metal and a decationised 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. Since lubricating oils are marketed in several grades with relatively narrow boiling ranges, distillation to give relatively ice 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 the hydrocatalytic treatment or distillation may take place before the hydrocatalytic treatment and individual cuts may be hydrotreated.
  • 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 reasphalted in the normal way.
  • the faujasite type zeolite used as starting material preferably has, in its dehydrated form, the formula:
  • a suitable synthetic zeolite of this type is Zeolite Y.
  • the zeolite is decationised, Le. a substantial proportion of the metal cations normally present have been removed giving a metal-cation deficiency.
  • This decationisation can be carried out in known manner.
  • sodium zeolite is base exchanged with ammonium cations.
  • the ammonium form is then heated to drive off ammonia, leaving behind the hydrogen form or decationised zeolite. It is possible that some of the hydrogen ions are also driven off leaving behind free sites in the crystal lattice, but this is not altogether clear.
  • the zeolite may be treated with a mineral acid, for example hydrochloric or sulphuric acid, in order directly to decationise the zeolite.
  • a combination of acid treatment and ammonium treatment can also be used.
  • the zeolite is decationised to an extent such that at least 50% wt. of the alkali metal cations are absent and more particularly at least -wt. It has been known for some time that the presence of alkali metal cations reduces the catalytic activity of zeolites. However, what is surprising in the present context is that other metal cations, which do not impair the hydrocracking acivity of the zeolite, nevertheless impair the ability of the zeolite to improve the viscosity index of lubricating oil fractions.
  • one zeolite hydrocracking catalyst uses a magnesium faujasite support and has good activity for cracking and good selectivity for gasoline production. Nevertheless its viscosity index improving characteristics are very much inferior to a catalyst based on decationised faujasite.
  • the hydrogenating metal on the zeolite is desirably a metal from Groups VI or VIII of the Periodic Table, particularly the latter.
  • a metal from Groups 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 after decationisation 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 form the amount of the metal should obviously not be such as to take up all the metal cation deficiency.
  • the preferred temperature is 350 to 390 C. and the preferred pressure 10000 to 13,800 kN./m. g.
  • Other process conditions for the hydrocatalytic treatment over the zeolite catalyst may be chosen from the following ranges:
  • the conversion should be less than wt. conversion to lower boiling products to give as one product a lubricating oil fraction boiling above 350 C.
  • the extent of conversion will depend on the relative amounts of gasoline and lubricating oil required and the desired viscosity index of the lubricating oil. Increased conversion increases the viscosity index of the lubricating oil but reduces its yield.
  • the conversion is preferably in the range 40-95% wt. conversion to products boiling below 350 C.
  • the zeolite catalysts used in the present invention are not permanently poisoned by sulphur and nitrogen compounds in the feedstock, but their activity is lowered. They are also tolerant of H 8 and NH produced from sulphur and nitrogen compounds by hydrocatalytic treatment, but again these products may reduce the overall activity. It is particularly preferred, therefore, to pretreat sulphur and nitrogen containing feedstocks and to remove H 8 and NH produced before passing the feedstock to the zeolite catalyst system.
  • the pretreatment is preferably catalytic hydrogenation.
  • Suitable catalysts comprise one or more hydrogenating metals on compounds thereof chosen from Groups VIa and VHI of the Periodic Table on an acidic refractory oxide support.
  • Suitable metals may be molybdenum together with one or more iron group metals, preferably from to 40% of molybdenum, calculated as the trioxide M00 and from 1 to of iron group metals, calculated as the divalent oxides (e.g. CoO or NiO).
  • the acidic support may be known catalytic cracking catalyst, for example catalysts of 50-95% wt. of silica and 5-50% wt. of alumina, or a support with more than 50% wt. of alumina and less than 50% wt.
  • Suitable catalysts may be chosen from the following ranges of composition
  • Suitable pretreatment conditions which are preferably chosen to give minimum breakdown to lower boiling products consistent with adequate sulphur and nitrogen removal, may be chosen from Temperature, C. 370 to 460 Pressure, kN./m. gauge 6.900 to 20,700 Space velocity, v./v./hr. 0.4 to 1.5 Hydrogen gas rate, mols/m. 25,000 to 75,000
  • the product from this pretreatment stage may be debutanised or topped to about 80 C. before passing to the zeolite catalyst system.
  • the sulphur content of the pretreatment stage normally liquid product is less than 500 p.p.m. wt., and the nitrogen content is less than 50 p.p.m. wt.
  • H 5 and NH produced may also be removed in conventional manner. In one hydrocracking system, however the H 5 and NH are not removed and pass with the pretreatment product to the first of two zeolite catalyst stages, the H 8 and NH being then removed after the first zeolite catalyst stage.
  • Such a system can be used if desired and, irrespective of whether H 8 and NH is removed, the zeolite catalyst system can be operated with 2 or more stages.
  • the lubricating oil product can be withdrawn from the system after any of the stages, although clearly, if withdrawn from the first or two zeolite catalyst stages only a portion of the product boiling above 350 C. should be withdrawn as lubricating oil product, the remainder passing to the second stage for further cracking.
  • 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 practised but it is not preferred. Starting with wax distillate fractions boiling in the range 350600 C. and having viscosity indices of 60-80, finished lubricating oil products with viscosity indices of -125 can be produced.
  • the gasoline produced is rich in iso-paraifins and naphthenes and may have a research octane number clear of the order of 85.
  • the amounnt of middle distillate boiling in the range 200 to 350 C. may be from 5 to 30% wt. of total product, the ratio of 15200 C. gasoline to 200- 350 C. middle distillate being from 1:1 to 10:1.
  • the invention is illustrated by the following comparative example.
  • the feedstock was a Kuwait wax distillate fraction having the following inspection data.
  • This feedstock was pretreated over a nickel-molybdenum-silica-alumina catalyst with the following inspection data.
  • the product was distilled to remove gas and low boiling hydrocarbon and a portion was analysed to determine the extent of conversion as follows:
  • a process for the production of lubricating oil and gasoline comprising contacting a petroleum feedstock boiling above 350 C. at a temperature of 350 to 420 0., a pressure of 6,900 to 26,700 k.N/m. g. and in the presence of hydrogen with a catalyst comprising a hydrogenating metal and a decationised zeolite of the faujasite type so that conversion to material boiling below 350 C. is from 40 to 95% wt., and recovering a product boiling TABLE 1 Pd-Mg- Pd-decationised Zeolite Y Zeolite Y Hours on str 446-458 514-526 552-564 590-602 625-637 Pressure, kN./m.
  • feedstock contains less than 500 p.p.m. wt. of sulphur and less than 50 p.p.m. wt. of nitrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (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)
US00145492A 1970-06-01 1971-05-20 Production of lubricating oils Expired - Lifetime US3732156A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB2630770 1970-06-01

Publications (1)

Publication Number Publication Date
US3732156A true US3732156A (en) 1973-05-08

Family

ID=10241587

Family Applications (1)

Application Number Title Priority Date Filing Date
US00145492A Expired - Lifetime US3732156A (en) 1970-06-01 1971-05-20 Production of lubricating oils

Country Status (7)

Country Link
US (1) US3732156A (OSRAM)
BE (1) BE767924A (OSRAM)
CA (1) CA946771A (OSRAM)
DE (1) DE2126603A1 (OSRAM)
FR (1) FR2093944B1 (OSRAM)
GB (1) GB1314879A (OSRAM)
NL (1) NL7107311A (OSRAM)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852207A (en) * 1973-03-26 1974-12-03 Chevron Res Production of stable lubricating oils by sequential hydrocracking and hydrogenation
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US3902988A (en) * 1973-02-09 1975-09-02 British Petroleum Co Production of lubricating oils
USB508118I5 (OSRAM) * 1974-09-23 1976-02-17
US4486296A (en) * 1983-10-13 1984-12-04 Mobil Oil Corporation Process for hydrocracking and dewaxing hydrocarbon oils
US20030174831A1 (en) * 2002-03-15 2003-09-18 Anthony Dezonno Transaction outcome state mapping
US20060104213A1 (en) * 2004-11-18 2006-05-18 Roger Sumner Discrete choice method of reporting and predicting multiple transaction types

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US3902988A (en) * 1973-02-09 1975-09-02 British Petroleum Co Production of lubricating oils
US3852207A (en) * 1973-03-26 1974-12-03 Chevron Res Production of stable lubricating oils by sequential hydrocracking and hydrogenation
USB508118I5 (OSRAM) * 1974-09-23 1976-02-17
US3992283A (en) * 1974-09-23 1976-11-16 Universal Oil Products Company Hydrocracking process for the maximization of an improved viscosity lube oil
US4486296A (en) * 1983-10-13 1984-12-04 Mobil Oil Corporation Process for hydrocracking and dewaxing hydrocarbon oils
US20030174831A1 (en) * 2002-03-15 2003-09-18 Anthony Dezonno Transaction outcome state mapping
US20060104213A1 (en) * 2004-11-18 2006-05-18 Roger Sumner Discrete choice method of reporting and predicting multiple transaction types

Also Published As

Publication number Publication date
DE2126603A1 (de) 1971-12-09
FR2093944B1 (OSRAM) 1974-03-08
GB1314879A (en) 1973-04-26
CA946771A (en) 1974-05-07
FR2093944A1 (OSRAM) 1972-02-04
NL7107311A (OSRAM) 1971-12-03
BE767924A (fr) 1971-12-01

Similar Documents

Publication Publication Date Title
CA1196879A (en) Hydrocracking process
US3668113A (en) Hydrocatalytic process for normal paraffin wax and sulfur removal
US5525209A (en) Process for the improved production of middle distillates jointly with the production of high viscosity oils with high viscosity indices from heavy petroleum cuts
US3730876A (en) Production of naphthenic oils
US6783661B1 (en) Process for producing oils with a high viscosity index
US4062758A (en) Process for the conversion of hydrocarbons in atmospheric crude residue
US3790472A (en) Hydrocracking process for producing lubricating oils
KR100240586B1 (ko) 수소첨가공정에서촉매기재로서적당한물질의조성물,이를포함한촉매조성물및이를기재로한수소전환방법
US2944005A (en) Catalytic conversion of hydrocarbon distillates
US3230164A (en) Hydrocracking process to produce gasoline and turbine fuels
US3308055A (en) Hydrocracking process producing lubricating oil
US3099617A (en) Pretreatment of catalyst employed in the hydrocracking of hydrocarbons
US3142635A (en) Production of lubricating oils
US2945801A (en) Catalytic cracking
US3732156A (en) Production of lubricating oils
US3726788A (en) Two-stage hydrocracking with intermediate fractionation
US3902988A (en) Production of lubricating oils
US5098551A (en) Process for the manufacture of lubricating base oils
US3804742A (en) Production of lubricating oils
US3663423A (en) Production of lubricating oils
US3272734A (en) Hydrofining and hydrocracking process
US3444071A (en) Process for the hydrogenative cracking of a hydrocarbon oil to produce lubricating oil
US3896025A (en) Production of improved lubricating oils
US3420768A (en) Middle distillate hydrogen treating processes
US3681232A (en) Combined hydrocracking and catalytic dewaxing process