Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/86—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/26—Chromium
• • 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
  • C10G35/00—Reforming naphtha
  • C10G35/04—Catalytic reforming
  • C10G35/06—Catalytic reforming characterised by the catalyst used
• • 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

Definitions

• Catalysts of chromium oxide on a support, for example, alumina are known to have dehydrogenating and dehydrocyclising properties and various promoters have been proposed for improving such catalysts.
• a process for the dehydrogenation or dehydrocyclisation of feedstocks consisting of or containing non-aromatic hydrocarbons comprises contacting the feedstock at a temperature of from 450 to 580 C. with a catalyst comprising chromium oxide on a support preferably alumina, the catalyst containing also a minor proportion (with respect to the chromium oxide) of beryllium and a minor proportion (with respect to chromium oxide) of an alkali metal, preferably potassium.
• the beryllium and the alkali metal are preferably present in the form oxides.
• Preferably minor amounts, with respect to the chormium oxide, of one or more other promoting elements are present also, for example nickel, or cobalt.
• a catalyst containing minor amounts of beryllium, potassium and nickel is particularly preferred.
• the preferred proportions of catalyst components, by weight of total catalyst stable at 550 C. are:
• the process is preferably carried out at a pressure of not more than 50 p.s.i.g. without the addition of extraneous hydrogen and without recycle of the hydrogencontaining gas produced in the process. An appreciable quantity of such gas is produced, which is available as a valuable by-product.
• the term not more than 5 O p.s.i.g. includes atmospheric pressure or below, atmospheric pressure being in fact preferred.
• the preferred space velocity is 0.1 to 1.0 v./v./hr.
• the catalyst may be used in the form of a fixed bed, a moving bed or a fluidised bed. Since it is readily regenerated by burning oif carbonaceous deposits in a stream of oxygen-containing gas it is particularly suitable for fluidised or moving bed processes.
• the feedstock used should boil within the gasoline or naphtha range (i.e. up to 200 C.) and may be pure hydrocarbons, for example straight chain paratfins or cycloparafi'ins, or mixtures of hydrocarbons. Preferably a major proportion of the feedstock boils below 100 C.
• the feedstock may be a straight-run gasoline fraction.
• gasolines or gasoline blending components having a research octane number (clear) of at least 90 may be obtained from such fractions.
• the products With feedstocks at the lower boiling end of the gasoline range the products will also have a high volatility and may be for example at least 50% volume evaporated at 100 C.
• a particularly preferred feedstock is a light gasoline having an end boiling point of about 80 to 120 C.
• the feedstock may be the product of a previous catalytic reforming process so that the present invention includes a two-stage reforming process designed to produce aromatics and high octane gasoline fractions with preferably a research octane number (clear) of the order of 100.
• Any convenient reforming process may be used as the first stage, but those employing a catalyst of platinum on a support containing aluminium oxide with or Without halogen are preferred, such processes being hereinafter referred to as platinum reforming processes and the products as platinum reformates.
• the whole of the reformate from the first stage may be reformed in the second stage.
• the reformate may be fractionated and a portion only subjected to the further treatment.
• the portion may be a lower boiling relatively aromatic free fraction, preferably one with an end boiling point below C. or a higher boiling fraction still containing some non-aromatic hydrocarbons.
• the reformate may be solvent extracted and the raflinate or a fraction thereof subjected to the further treatment.
• the product may be recombined with the untreated fraction or the solvent extract as the case may be, but it may also be combined with other high octane components, for example heavy cat. cracked gasoline or alkylate.
• the catalyst may be prepared by any convenient method.
• the base may be impregnated with all the constituents together, or two or more solutions containing different constituents may be used in succession.
• the impregnated base is dried and calcined.
• the alumina base may be co-precipitated from a solution, containing aluminium and either chromium or beryllium or both, with alkali, and the precipitate Washed, dired, and calcined.
• the alkali metal may be subsequently added by impregnation, together with any constituent not co-precipitated.
• the catalyst is then again dried and calcined.
• An insoluble chromium or beryllium compound or both may be milled into the alumina base, further constituents added by impregnation and the catalyst dried and calcined.
• the present invention includes a catalyst comprising chromium oxide on a support, preferably alumina, the catalyst containing also a minor proportion (with respect to the chromium oxide) of beryllium and a minor proportion (with respect to the chromium oxide) of an alkali metal, preferably potassium.
• the beryllium and .the alkali metal are preferably present in the form of oxides.
• the catalyst may contain minor amounts of one or more other promoters as detailed above and the preferred proportions of catalyst components are also as set out above.
• EXAMPLE 1 A solution containing 24 g. Analar chromium trioxide, 4 g. Analar potassium nitrate (KNO 5.5 g. beryllium nitrate [Be(NO .3H O] and 3 g. Analar" nickel nitrate [Ni(NO .6H O] was used to impregnate 160 g. of alumina which had previously been calcined at 550 C. for two hours. The impregnated alumina was then dried for one hour at C. and calcined for two hours at 550 C.
• EXAMPLE 2 A solution containing 24 g. Analar chromium trioxide, 4 g. Analar potassium nitrate (KNO 14 g. beryllium nitrate [Be(NO .3H O], 3.5 g. Analar cobalt nitrate [Co(NO .6H O] and 3.5 g. Analar nickel nitrate [Ni(NO .6H O] was used to impregnate 160 g. of alumina which had previously been calcined at 550 C. for two hours. The impregnated alumina was then dried for one hour at 130 C. and calcined for two hours 10 at 550 C.
• Runs were carried out at two temperatures-475 C. and 530 C.
• a process for the treatment of a petroleum feedstock consisting essentially of non-aromatic hydrocarbons boiling within the range encompassed by the gasoline and naphtha range to produce a product having an increased aromatic content comprising contacting the feedstock in a reaction zone with a catalyst consisting essentially of 5 to of chromium oxide, expressed as Cr O 0.1 to 5% of beryllium, expressed as BeO; 0.11 to 5% of an alkali metal, expressed as alkali metal oxide, about 0.1 to 5% of nickel, expressed as NiO; about 0.1 to 5% of cobalt, expressed as C00, and balance alumina, all percentages being by weight of total catalyst material stable at 550 C., at a temperature of 450 to 580 C., at a pressure not in excess of about p.s.i. ga., at a space velocity of 0.1 to 1.0 v./v./hr., and in the absence of Table 3 Reaction temperature 475 0. 530 C.
• a process for the treatment of a petroleum feedstock consisting essentially of non-aromatic hydrocarbons boiling within the range encompassed by the gasoline and naphtha range to produce a product having an increased aromatic content comprising contacting the feedstock in a reaction zone with a catalyst consisting essentially of 5 to 25% of chromium oxide, expressed as Cr O 0.1 to 5% of beryllium, expressed as BeO; 0.1 to 5% of an 0 alkali metal, expressed as alkali metal oxide, about 0.1 to 5% of nickel, expressed as NiO, and balance alumina,

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

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Cited By (5)

Citations (6)

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• 0
  • BE BE581979D patent/BE581979A/xx unknown
• 1958
  • 1958-08-27 GB GB27463/58A patent/GB857504A/en not_active Expired
• 1959
  • 1959-08-18 US US834404A patent/US3114697A/en not_active Expired - Lifetime
  • 1959-08-24 FR FR803410A patent/FR1233404A/fr not_active Expired
  • 1959-08-26 DE DEB54558A patent/DE1107862B/de active Pending

Patent Citations (6)

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