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
  • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
  • C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
  • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition

Definitions

• This invention relates to the treatment of the products of a catalytic reforming process, hereinafter referred to as catalytic reformates.
• a naphtha fraction is contacted at elevated temperature and pressure and in the presence of hydrogen with a dehydrogenation catalyst to produce a gasoline fraction of increased octane number.
• Catalysts that are used commercially include molybdenum oxide on alumina and catalysts consisting essentially of platinum on alumina with or without combined halogen.
• a catflytic reforming process using a platinum-onalumina type catalyst will hereinafter be referred to as platinum reforming and the products as platinum reformates.
• Platinum reforming is capable of giving products with octane numbers research (clear) of the order of 90-100, but it has certain limitations.
• increase in octane number is only obtainable at the expense of decreased volatility and this runs contrary to the present emphasis on gasolines having both high octane number and high volatility.
• adjustment of the feedstock boiling range can improve product volatility, treatment of lower-boiling feedstocks requires high operating severity and gives lower yields.
• there is a practical upper limit of octane number quite irrespective of volatility.
• a catalytic reformate is separated into a higher-boiling fraction and a lower-boiling fraction, at least the higher-boiling fraction is contacted at from 840 to 1075 F. (450 to 580 C.) with a dehydrogenation and dehydrocyclisation catalyst to yield a product of increased volatility and the treated higher-boiling fraction is recombined either with the untreated lower-boiling fraction or with the lower-boiling fraction after it has also been contacted at elevated temperature with a dehydrogenation and dehydrocyclisation catalyst to yield a product of increased octane number.
• the higher-boiling fraction of a catalyst reformate is relatively rich in aromatics andis not, prima facie, a suitable material for further upgrading by dehydrogenation and dehydrocyclisation.
• a treatment gives a product of increased volatility.
• the octane number can also be increased further.
• a final product is obtained of increased volatility and also, usually, increased octane number.
• the product has a volatility of at least 40% volume evaporated at 100 C., particularly from 40 to 60%, and an octane number research (clear) of at least 90.
• the product may be used as a component of motor gasolines, but the process is particularly suitable for the production of high octane number, high volatility motor gasolines themselves which do not require the addition of further blending components.
• both the higher-boiling'and the lower boiling fractions are contacted separately with a dehydrogenation and dehydrocyclisation catalyst and the fractions are re-combined.
• the recombined blend has an octane number research (clear) of at least 100. It has been found that higher octane numbers are obtain- 3,033,777 Patented May 8, 1902 able at a given reactionv temperature when compared with a single treatment of the whole of a catalytic reformate.
• the preferred dehydrogenation and dehydrocyclisation catalyst for treating both the higher-boiling and lower boiling fractions consists essentially of chromium oxide supported on alumina. It is preferably used ata pressure of up to 50 p.s.i.g. (including atmospheric pressure or below) and without recycle of the hydrogen-rich gas produced or addition of extraneous hydrogen-rich gas produced or addition of extraneous hydrogen.
• the space velocity may be from 0.1 to 1.0 v./v./hr. of liquid feedstock.
• the chromia on alumina catalyst may contain a minor proportion of oneor more promoters, for example a rare earth or mixture of rare earths,- bismuth, boron, germanium, nickel, man anese, iron or beryllium preferably in combination with an alkali metal, such, as potassium.
• promoters for example a rare earth or mixture of rare earths,- bismuth, boron, germanium, nickel, man anese, iron or beryllium preferably in combination with an alkali metal, such, as potassium.
• Another particularly etfective promoter is a minor proportion of a spinel, for example cobalt, chromite, copper chromite, zinc titanate, or iron chromite, either as such or in the form of the naturally-occurring ore chrome ironstone.
• Total promoters (expressed as oxide in the case of The dehydrogenation and dehydrocyclisation process may be carried out with a fixed bed, a moving bed or a fluidised bed of catalyst. With the preferred catalyst,
• the preferred catalytic reformate used as feed stock is a platinum reformate.
• the platinum reformate is preferably produced by a platinum reforming process using a heavy naphtha'feedstock and operating under conditions such that regeneration of the catalyst in situ is not required (i.e. a catalyst life of at least 40 barrels of feedstock processed per lb. of catalyst).
• heavy naphtha means anaphtha having an ASTM final. boiling point between 150 C. and 200 C. and, preferably, an ASTM initial boiling point within the range 70 C. to C. p
• the platinum reforming stage is preferably operated to give a reformate having an octane number research (clear) of'90 to 100. Any convenient platinurnreforming process may be used and the process conditions will normall'yifall within'the following ranges:
• Temperature 60.0 1200 preferably 9004000 F. 504000 p.s'.i., preferably 300-700 7 characteristics shown in Table 2.
• The'higher-boiling fraction of the catalytic reformate should contain the majority of the alkyl aromatics in the reformate.
• a convenient separation point is in the range 80l30 0., more particularly within the range 100-120 C. The separation may be efiected by simple distillation.
• EXAMPLE 1 i A naphtha of Middle East origin having an ASTM boiling range of 90-171" C. was reformed using a catalyst of 0.7% wt. platinum, 0.45% Wt. fluorine and 0.34% wt. chlorine on alumina to a research octane level of 93.
• the reforming conditions used were 925 F., 500' p.s.i.g., 10 v./v./hr. and a hydrozen/hydrocarbon'mol 'ratio of 10:1.
• the platinum reiormate so produced was fractionated at 100 C. to 'give a lower-boiling fraction having an ASTM boiling range of 43 97.5 C.
• the lower-boiling fraction represented 34.4% wt. and the higher-boiling fraction 65.6% wt. of the platinum reformate.
• the higher-boiling fraction was treated over a fixed bed of a catalyst consisting of 10% Wt. chromia on alumina promoted with 1% wt. cerium oxide and 1% wt.
• Runs were carried out at two different temperatures lower-boiling fraction having an ASTM boiling range of 34-108 C. and an octane number research (clear) of 76.1 and a higher-boiling fraction having an ASTM boiling range of 128-216 C., and an octane number research (clear) of 104.6.
• the lower-boiling fraction represented 41.2% wt. and the higher-boiling fraction 58.8% wt. of the platinum reformate.
• the higher-boiling fraction was treated under the same conditions and with the same catalyst as that used in Example 1.
• Octane number research (clea Blend of treated hlgherand lower-boiling fractions-Blended in make ratio on total reiormate Yield on total relormate, percent From the table it will be seen that at a reaction temperature of 887 F. the blended product has a somewhat higher octane number and a considerably higher volatility than the treated total reformate. At the higher reaction temperatures the two products are of equivalent volatility but the blended product has a considerably higher octane number.
• a process for the treatment of a catalytic reformate to produce a product having a high octane number and high volatility which comprises separating the catalytic reformate into a high boiling fraction and a low boiling fraction, the cut point between the fractions being in the range 80 to 130 C., contacting the high boiling fraction in a reaction zone with a dehydrogenation and dehydrocyclization catalyst consisting essentially of to 25% wt. of chromium oxide by weight of total catalyst stable at 1020 F., and balance alumina, at a temperature of 840 to 1075 F., at a pressure not in excess of 50 p.s.i.
• a process for the treatment of a catalytic reformate to produce a product having a high octane number and high volatility which comprises separating the catalytic reformate into a high boiling fraction and a low boiling fraction, the cut point between the fractions being in the range 80 to 130 C., contacting the high boiling fraction in a reaction zone with a dehydrogenation and dehydrocyclization catalyst consisting essentially of 5 to 25% wt. of chromium oxide, by weight of total catalyst stable at to 1075 F., at a pressure not in excess of p.s.i.
• a dehydrogenation and dehydrocyclization catalyst consisting essentially of 5 to 25% wt. of chromium oxide, by weight of total catalyst stable at 1020 F., and balance alumina, at a temperature of 840 to 1075 F., at apressure not in excess of 50 p.s.i.
• the catalyst includes at least one promoter in an amount of 0.1 to 10% wt. by weight of total catalyst stable at 1020 F., said weight of promoter being less than the weight of the chromium oxide.
• the catalyst includes at least one promoter in an amount of 0.1 to 10% wt. by weight of total catalyst stable at 1020" F., said weight of promoter being less than the weight of the chromium oxide.
• catalytic reformate is a platinum reformate.
• Tabtl e E3 heading to column 2 thereof for "Feed F.” read Signed and sealed this 9th day of October 1962.

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

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Citations (6)

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• 0
  • BE BE578938D patent/BE578938A/xx unknown
• 1958
  • 1958-05-23 GB GB16609/58A patent/GB871756A/en not_active Expired
• 1959
  • 1959-05-06 FR FR794159A patent/FR1227548A/fr not_active Expired
  • 1959-05-11 US US812139A patent/US3033777A/en not_active Expired - Lifetime
  • 1959-05-22 DE DEB53322A patent/DE1102945B/de active Pending

Patent Citations (6)

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