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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
  • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes

Definitions

• This invention relates to a process for converting olefins to distillate and/or lube oil products.
• U.S. Patent No. 4,150,062 describes a process for the conversion of olefins having 2 to 4 carbon atoms to a product comprising a high octane gasoline component by contacting an appropriate olefin feedstock with a catalyst comprising a crystalline aluminosilicate zeolite in the presence of a relatively large amount of water.
• U.S. Patent No. 4,211,640 describes a catalytic process for the treatment of highly olefinic gasoline with an acidic crystalline aluminosilicate zeolite to enhance the gum stability of said gasoline and produce products comprising both gasoline and fuel oil.
• the present invention is predicated on the discovery that when low molecular weight aromatic compounds are added to an olefin-to- gasoline/distillate (OG/D) reaction product stream, the olefinic components in the stream will alkylate the aromatics to form both lube and diesel range materials. Lube oil produced thereby is in increased yield and viscosity index.
• O/D olefin-to- gasoline/distillate
• the present invention resides in a process for converting olefins to distillate and/or lube oil products, comprising contacting under conversion conditions an olefin with a crystalline aluminosilicate zeolite having a silica to alumina mole ratio of at least 12 and a constraint index within the range of 1 to 12 in a reaction zone in the presence of a reactive aromatic hydrocarbon; said olefin and said reactive aromatic hydrocarbon being present in the molar ratio of 10:1 to 1:1.
• the olefins used in the present process may be any of those employed in conventional OG/D technology and include mono- and diolefins of 2 to 10 carbon atoms, such as ethene and propene; cycloolefins of 3 to 10 carbon atoms, such as cyclobutene and cyclopentene; and olefins alkylated to aromatic rings with less than 10 carbon atoms.
• Preferred olefins have 2 to 7 caroon atoms.
• reactive olefinic products of OG/D reactions can be used as the feed stream in the present process.
• the aroaiatic compounds may be added directly to the reaction zone with the unreacted olefin or it may be added to the reaction zone after the olefin-to- gasoline/distillate reaction has had an opportunity to provide some long-chain olefins.
• a product of increased lube yield and, higher viscosity index will be provided. Because of the high value of lube oil relative to lighter distillate, there is incentive to maximize lube product.
• the aromatic hydrocarbons used in the present process may contain one or two aromatic rings, including aromatic rings alkylated with one or more saturated or unsaturated groups, and including aromatic rings connected to saturated rings, such as tetralin, methyltetralin and ethyltetralin.
• aromatic rings alkylated with one or more saturated or unsaturated groups
• aromatic rings connected to saturated rings such as tetralin, methyltetralin and ethyltetralin.
• aromatics such as a reformate cut. If a stream rich in both olefins and aromatics, such as an FC C gasoline, is used the olefins will also take part in the olefin- to-gasoline/distillate reaction.
• the catalyst used in the present process is a crystalline aluminosilicate zeolite having a silica to alumina mole ratio of at least 12 and a constraint index of 1 to 12.
• a zeolite examples include ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38.
• Zeolite ZSM-5 is described in U.S. Patent No. 3,702,886;
• ZSM-11 is described in U.S. Patent No. 3,709,979;
• ZSM-12 is described in U.S. Patent No. 3,838,449;
• ZSM-35 is described in U.S. Patent No. 4,016,245; and
• ZSM-38 is described in U.S. Patent No. 4,046,859.
• natural zeolites may sometimes be converted to this type zeolite catalyst by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination or some combination thereof.
• Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite and clinoptilolite.
• the preferred crystal aluminosilicate zeolites are ZSM-5 and ZSM-12.
• the zeolite catalyst is employed in combination with a support or a binder, such as for example, a porous inorganic oxide support or a clay binder.
• binder materials include alumina, zirconia, silica, magnesia, thoria, titania, boria and combinations thereof, generally in the form of dried inorganic oxide gels and gelatinous precipitates.
• Suitable clay materials include, by way of example, bentonite and kieselguhr.
• the amount of aluminosilicate zeolite to the total composition of catalyst and binder or support may vary between 30% to 90% by weight, and more usually in the range of 50% to 80% by weight of the composition.
• the operating conditions employed in the present process particularly the temperature, pressure, space velocity, molar ratio of aromatic to olefin reactants, absence of added hydrogen, and the presence of any diluents are chosen so to promote reaction between the aromatics and the OG/D product distillate to produce long-chain alkyl aromatics and thereby increase lube oil yield and viscosity index.
• Suitable operating conditions include a temperature from 204 to 427°C (400 to 800°F), a pressure from 791 to 17339 kPa (100 to 2500 psig), and a LHSV from 0.2 to 20 per hour.
• Preferred conditions include a temperature from 232 to 316°C (450 to 600°F), a pressure from 4238 to 6990 kPa (600 to 1000 psig), and a LHSV from 0.5 to 2 and most preferably from 1 to 1.5.
• the molar ratio of olefins to reactive aromatic hydrocarbon may vary from 10:1 to 1:1.
• reactive hydrocarbons are aromatic hydrocarbons and alkyl-substituted cyclic hydrocarbons, or alkyl aromatic cyclic hydrocarbons. Also, if desired, any suitable diluent known in the art may be used.
• Table 1 shows the effect on viscosity index of adding alkyl chains to both single and dicyclic aromatics.
• Table 1 shows the effect on viscosity index of adding alkyl chains to both single and dicyclic aromatics.
• the highest viscosity indices are achieved by adding long straight alkyl chains, but some viscosity index improvement is obtained with highly substituted compounds.
• An OG/D distillate having the following properties was produced by reaction of a C 3 -C 4 olefin over an H-ZSM-12 extrudate catalyst containing 65% of the zeolite with a SiO 2 /Al 2 O 3 molar ratio of 123:1 and 35% of an alumina binder at 232°C (450°F) and 4238 kPa (600 psig).
• Table 2 compares the results obtained by contacting the resultant distillate with the same ZSM-12 catalyst at a LHSV of 1.0 and a pressure of 1000 psig (6996 kPa) with and without the addition of an aromatic compound in the form of benzene.

Landscapes

• 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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (2)

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Cited By (5)

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• 1983
  • 1983-07-29 CA CA000433564A patent/CA1228561A/en not_active Expired
  • 1983-08-01 AU AU17488/83A patent/AU1748883A/en not_active Abandoned
  • 1983-08-02 EP EP83304451A patent/EP0104729A3/de not_active Withdrawn
  • 1983-08-09 ZA ZA835854A patent/ZA835854B/xx unknown
  • 1983-09-28 JP JP58178356A patent/JPS5980490A/ja active Pending

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