EP0770666B1 - Two step process for upgrading of cyclic naphthas - Google Patents

Two step process for upgrading of cyclic naphthas Download PDF

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Publication number
EP0770666B1
EP0770666B1 EP19950117015 EP95117015A EP0770666B1 EP 0770666 B1 EP0770666 B1 EP 0770666B1 EP 19950117015 EP19950117015 EP 19950117015 EP 95117015 A EP95117015 A EP 95117015A EP 0770666 B1 EP0770666 B1 EP 0770666B1
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Prior art keywords
cleavage
ring
isomerization
catalyst
nonacidic
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German (de)
English (en)
French (fr)
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EP0770666A1 (en
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B. Galperin
Jeffery C. Bricker
Jennifer S. Holmgren
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Honeywell UOP LLC
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UOP LLC
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Priority to ES95117015T priority Critical patent/ES2158026T3/es
Priority to DE1995621319 priority patent/DE69521319T2/de
Priority to EP19950117015 priority patent/EP0770666B1/en
Priority to DK95117015T priority patent/DK0770666T3/da
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    • 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

  • This invention relates to an improved process for the selective upgrading of naphtha fractions containing naphthenes by a combination of a high conversion ring cleavage step and an isomerization step.
  • Reformulated gasoline differs from the traditional product in having a lower vapor pressure, lower final boiling point, increased content of oxygenates, and lower content of olefins, benzene and aromatics.
  • Benzene content will be restricted to 1% or lower.
  • Gasoline aromatics content is likely to be lowered into the 20-25% range in major urban areas, and low-emission gasoline containing less than 15 volume% aromatics is being advocated for some areas with severe pollution problems. Distillation end points (usually characterized as the 90% distillation temperature) also could be lowered, further restricting aromatics content since the high-boiling portion of the gasoline which thereby would be eliminated usually is an aromatics concentrate.
  • US-A-4783575 discloses ring opening of at least 40% within an isomerization unit using a high-chloride platinum-alumina catalyst in multiple reaction zones; this approach does not recognize the effect of feed cyclics conversion on the activity of the acidic isomerization catalyst.
  • US-A-2915571 discloses an isomerization process followed by separation and ring-opening of cyclic hydrocarbons using a supported iron-group-metal catalyst.
  • US-A-3457162 teaches conversion of cyclic hydrocarbons in jet fuel to straight-chain and slightly branched paraffins using a catalyst comprising an inorganic oxide, platinum-group metal and combined chloride; the reaction is carried out at a pressure substantially in excess of 6895 kPa (1000 psi).
  • International patent application WO 93/08145 discloses the processing of a hydrocarbon feedstock by ring opening using a zeolitic catalyst followed by isomerization of paraffins; zeolites are characterized by Constraint Index.
  • a specific object is to address issues faced by petroleum refiners who are modifying isomerization feedstocks to produce reformulated gasoline.
  • This invention is based on the discovery that certain nonacidic catalysts are particularly effective for napthene ring cleavage, which, when combined with paraffin isomerization, provides improved gasoline octane values.
  • a broad embodiment of the present invention is directed to a process using a ring-cleavage step in which a nonacidic catalyst containing a platinum-group metal is used to cleave rings in a naphtha feedstock to produce paraffins.
  • ring cleavage is effected prior to isomerization of paraffins in the product of the ring-cleavage step. More preferably, ring cleavage and isomerization are accomplished in the same hydrogen circuit.
  • isoparaffin-rich product from isomerization is fractionated to separate a naphthene-rich fraction which is recycled to the ring-cleavage step.
  • the Figure shows a simplified illustration of a flowscheme comprising ring cleavage, isomerization, and separation of a heavy fraction as recycle to ring cleavage.
  • the ring-cleavage step of the present invention is observed to be particularly useful in combination with isomerization of light paraffins.
  • the proportion of catalyst available for isomerization of paraffins is increased since cyclics have a detrimental effect on isomerization catalyst activity as explained herein.
  • a variety of nonacidic catalysts, process conditions and configurations are effective for opening of rings.
  • Ring cleavage also may be used in conjunction with other processes, e.g., selective isoparaffin synthesis to produce isobutane and other valuable products from middle-range and heavy naphthas.
  • process combinations are integrated into a petroleum refinery comprising crude-oil distillation, reforming, cracking and other processes known in the art to produce finished gasoline and other petroleum products.
  • ring cleavage may be used in combination with other processes, ring cleavage and isomerization preferably are combined as shown in the Figure.
  • This diagram provides an overview of the process.
  • the naphthene-containing naphtha feedstock is charged via line 11, along with hydrogen via line 12, to the ring-cleavage zone 10 which subjects naphthenic rings to ring-cleavage conditions in the presence of a ring-cleavage nonacidic catalyst to produce a paraffinic intermediate in line 14.
  • Light gases produced in the ring-cleavage zone may either be removed via line 13 if the ring-cleavage and subsequent isomerization zones have separate hydrogen circuits or passed into the isomerization zone in combination with the paraffinic intermediate if the two zones are contained in a single hydrogen circuit.
  • the paraffinic intermediate is transferred via line 14 to a isomerization zone 20 which preferably is contained within the same hydrogen circuit as the ring-cleavage zone, i.e., hydrogen and light hydrocarbons are not separated from the paraffinic intermediate before entering the isomerization zone.
  • This single circuit obviates the need for two sets of heat exchangers, separators and compressors for hydrogen-rich gas.
  • the paraffinic intermediate thus also may be transferred to the isomerization zone at an increased temperature resulting from the exothermic heat of reaction of ring opening and aromatics hydrogenation. In this manner, heating of the paraffinic intermediate optimally is not required.
  • the paraffinic intermediate is converted to yield more-highly-branched paraffins at isomerization conditions over a selective solid acid isomerization catalyst.
  • Small amounts of light gases are separated by flash and/or fractionation and removed via line 22, and an isoparaffin-rich product is obtained via line 23.
  • the product optionally passes to fractionator 30 which separates an isoparaffin concentrate via 31.
  • fractionator 30 which separates an isoparaffin concentrate via 31.
  • a cyclics concentrate is removed from near or at the bottom of the fractionator via line 32 and recycled to the ring-cleavage zone 10 via line 32. It is within the scope of the invention that the feedstock passes directly to isomerization via line 14, with the total feed to ring cleavage being the cyclics concentrate in line 32.
  • Naphtha feedstock to the present process comprises paraffins, naphthenes, and aromatics, and may comprise small amounts of olefins, boiling within the gasoline range.
  • Feedstocks which may be utilized include straight-run naphthas, natural gasoline, synthetic naphthas, thermal gasoline, catalytically cracked gasoline, partially reformed naphthas or raffinates from extraction of aromatics.
  • the feedstock essentially is encompassed by the range of a full-range naphtha, or within the range of 0° to 230°C.
  • the feedstock is light naphtha having an initial boiling point of about 10° to 65°C and a final boiling point from about 75° to 110°C; preferably, the final boiling point is less than about 95°C.
  • the naphtha feedstock generally contains small amounts of sulfur compounds amounting to less than 10 mass parts per million (ppm) on an elemental basis.
  • the naphtha feedstock has been prepared from a contaminated feedstock by a conventional pretreating step such as hydrotreating, hydrorefining or hydrodesulfurization to convert such contaminants as sulfurous, nitrogenous and oxygenated compounds to H 2 S, NH 3 and H 2 O, respectively, which can be separated from hydrocarbons by fractionation.
  • the pretreating step will provide the instant process combination with a hydrocarbon feedstock having low sulfur levels disclosed in the prior art as desirable, e.g., 1 mass ppm to 0.1 ppm (100 ppb). It is within the ambit of the present invention that this optional pretreating step be included in the present process combination.
  • the principal components of the preferred feedstock are alkanes and cycloalkanes having from 4 to 7 carbon atoms per molecule (C 4 to C 7 ), especially C 5 to C 6 , and smaller amounts of aromatic and olefinic hydrocarbons also may be present.
  • C 4 to C 7 carbon atoms per molecule
  • the concentration of C 7 and heavier components is less than about 20 mass % of the feedstock.
  • the feedstock generally contains between about 2 and 40 mass % of cyclics comprising naphthenes and aromatics.
  • the aromatics contained in the naphtha feedstock may comprise from 2 to 20 mass % and more usually 5 to 10 mass % of the total.
  • Benzene usually comprises the principal aromatics constituent of the preferred feedstock, optionally along with smaller amounts of toluene and higher-boiling aromatics within the boiling ranges described above.
  • the aromatics generally are not hydrogenated to naphthenes to a large extent in a naphtha pretreating process as described above, and thus mostly remain in the feed to the ring-cleavage step.
  • aromatics in the feed to an isomerization process are essentially quantitatively hydrogenated, the resulting exothermic heat of reaction can affect the temperature profile of the isomerization to a significant extent. Most or substantially all of the aromatics are beneficially hydrogenated in conjunction with the ring-opening reaction, prior to isomerization in the ring-cleavage zone of the present invention, thus enabling more precise control of isomerization temperature.
  • Naphtha feedstock and hydrogen comprise combined feed to the ring-cleavage zone, which contains a nonacidic ring-cleavage catalyst and operates at suitable conditions to open naphthenic rings to form paraffins without a high degree of conversion to lighter products.
  • the ring-cleavage catalyst comprises one or more platinum-group metals, selected from the group consisting of platinum, palladium, ruthenium, rhodium, osmium, and iridium, on a nonacidic support comprising one or more of a refractory inorganic-oxide and a large-pore molecular sieve.
  • the "nonacidic support" has a substantial absence of acid sites, for example as an inherent property or through ion exchange with one or more basic cations.
  • the nonacidity of the ring-cleavage support may be determined using a variety of methods known in the art.
  • a preferred method of determining acidity is the heptene cracking test as described below. Conversion of heptene, principally by cracking, isomerization and ring formation, is measured at specified conditions. Cracking is particularly indicative of the presence of strong acid sites.
  • a nonacidic catalyst suitable for ring cleavage demonstrates low conversion and particularly low cracking in the heptene test: conversion generally is less than 30% and cracking less than about 5%. The best supports demonstrate no more than about 5% conversion and negligible cracking.
  • the heptene cracking test also is effected in an atmospheric microreactor.
  • an electrically heated reactor is loaded with 250 mg of 0.25 to 0.420 mm (40-60 mesh) particles made by crushing the sample particles.
  • Each catalyst is dried in situ for 30 minutes at 200°C using flowing hydrogen.
  • the catalyst is then subjected to a reduction treatment for one hour at 550°C in flowing hydrogen.
  • the reactor is then brought to the desired operational temperature of 425°C (inlet).
  • the feed stream to the reactor comprises hydrogen gas saturated with 1-heptene at 0°C and ambient atmospheric pressure.
  • the inlet temperature is held constant while the flow rate of the 1-heptene saturated hydrogen is varied in a predetermined pattern.
  • Analysis is performed by analyzing the effluent using a gas chromatograph. Samples for analysis are automatically taken after 15 minutes of onstream operation at 250 cc/min. feed gas flow, at 45 minutes with the feed flowrate at 500 cc/min., at 75 minutes with the feed gas flowrate at 1000 cc/min., at 105 minutes with the feed gas flowrate at 125 cc/min.
  • nonacidity may be characterized by the ACAC (acetonylacetone) test.
  • ACAC acetonylacetone
  • dimethylfuran in the product is an indicator of acidity
  • methylcyclopentenone indicates basicity.
  • Conversion over the support of the invention during a 5-minute period at 150°C at a rate of 100 cc/min should yield less than 5 mass %, and preferably less than 1%, acid products. Conversion to basic products can usefully be in the range of 0-70 mass %.
  • NH 3 -TPD temperature-programmed desorption
  • the NH 3 -TPD acidity strength should be less than about 1.0.
  • Other methods such as 31 P solids NMR of adsorbed TMP (trimethylphosphine) also may be used to measure acidity.
  • the preferred nonacidic support optimally comprises a porous, adsorptive, high-surface-area inorganic oxide having a surface area of 25 to 500 m 2 /g.
  • the porous support should also be uniform in composition and relatively refractory to the conditions utilized in the process.
  • uniform in composition it is meant that the support be unlayered, has no concentration gradients of the species inherent to its composition, and is completely homogeneous in composition.
  • the support is a mixture of two or more refractory materials, the relative amounts of these materials will be constant and uniform throughout the entire support.
  • refractory inorganic oxides such as alumina, titania, zirconia, chromia, zinc oxide, magnesia, thoria, boria, silica-alumina, silica-magnesia, chromia-alumina, alumina-boria, silica-zirconia and other mixtures thereof.
  • the preferred refractory inorganic oxide for use in the present invention comprises alumina.
  • Suitable alumina materials are the crystalline aluminas known as the theta-, alpha-, gamma-, and eta-alumina, with theta-, alpha-, and gamma-alumina giving best results.
  • Magnesia alone or in combination with alumina, comprises an alternative inorganic-oxide component of the catalyst and provides the required nonacidity.
  • the preferred refractory inorganic oxide will have an apparent bulk density of 0.3 to 1.1 g/cc and surface area characteristics such that the average pore diameter is 20 to 1000 angstroms, the pore volume is about 0.05 to 1 cc/g, and the surface area is 50 to 500 m 2 /g.
  • the inorganic-oxide powder may be formed into a suitable catalyst material according to any of the techniques known to those skilled in the catalyst-carrier-forming art.
  • Spherical carrier particles may be formed, for example, from the preferred alumina by: (1) converting the alumina powder into an alumina sol by reaction with a suitable peptizing acid and water and thereafter dropping a mixture of the resulting sol and a gelling agent into an oil bath to form spherical particles of an alumina gel which are easily converted to a gamma-alumina support by known methods; (2) forming an extrudate from the powder by established methods and thereafter rolling the extrudate particles on a spinning disk until spherical particles are formed which can then be dried and calcined to form the desired particles of spherical support; and (3) wetting the powder v'ith a suitable peptizing agent and thereafter rolling the particles of the powder into spherical masses of the desired size.
  • the powder can also be formed in any other desired shape or type of support
  • the preferred form of carrier material for the ring-cleavage catalyst is a cylindrical extrudate.
  • the extrudate particle is optimally prepared by mixing the preferred alumina powder with water and suitable peptizing agents such as nitric acid, acetic acid, aluminum nitrate, and the like material until an extrudable dough is formed.
  • suitable peptizing agents such as nitric acid, acetic acid, aluminum nitrate, and the like material until an extrudable dough is formed.
  • the amount of water added to form the dough is typically sufficient to give a Loss on Ignition (LOI) at 500°C of 45 to 65 mass %, with a value of 55 mass % being especially preferred.
  • LOI Loss on Ignition
  • the resulting dough is then extruded through a suitably sized die to form extrudate particles.
  • the extrudate particles are dried at a temperature of about 150° to 200°C, and then calcined at a temperature of about 450° to 800°C for a period of 0.5 to 10 hours to effect the preferred form of the refractory inorganic oxide.
  • the catalyst be non-acidic, as acidity in the zeolite lowers the selectivity to paraffins of the finished catalyst.
  • the required nonacidity may be effected by any suitable method, including impregnation, co-impregnation with a platinum-group metal, or ion exchange. Impregnation of one or more of the alkali and alkaline earth metals, especially potassium, in a salt solution is favored as being an economically attractive method.
  • the metal effectively is associated with an anion such as hydroxide, nitrate or a halide such as chloride or bromide consistent with nonacidity of the finished catalyst, with a nitrate being favored.
  • the support is cold-rolled with an excess of solution in a rotary evaporator in an amount sufficient to provide a nonacidic catalyst.
  • the alkali or alkaline earth metal may be coimpregnated along with a platinum-group metal component, as long as the platinum-group metal does not precipitate in the presence of the salt of the alkali or alkaline earth metal.
  • Ion exchange is an alternative method of incorporating nonacidity into the catalyst.
  • the inorganic-oxide support is contacted with a solution containing an excess of metal ions over the amount needed to effect nonacidity.
  • a solution containing an excess of metal ions over the amount needed to effect nonacidity.
  • an effective method is to circulate a salt solution over the support in a fixed-bed loading tank.
  • a water-soluble metal salt of an alkali or alkaline earth metal is used to provide the required metal ions; a potassium salt is particularly preferred.
  • the support is contacted with the solution suitably at a temperature ranging from about 10° to about 100°C.
  • Synthetic hydrota!cite characterized as a layered double hydroxide or metal-oxide solid solution.
  • Hydrotalcite is a clay with the ideal unit cell formula of Mg 6 Al 2 (OH) 16 (CO 3 ) ⁇ 4H 2 O, and closely related analogs with variable magnesium/aluminum ratios may be readily prepared.
  • W. T. Reichle has described in the Journal of Catalysis, 94 , 547-557 (1985), the synthesis and catalytic use of such synthetic hydrotalcites, including materials having Mg and Al replaced by other metals. Calcination of such layered double hydroxides results in destruction of the layered structure and formation of materials which are effectively described as solid solutions of the resulting metal oxides.
  • M +2 is a divalent metal or combination of divalent metals selected from the group consisting of magnesium, calcium, barium, nickel, cobalt, iron, copper and zinc.
  • M +3 is a trivalent metal or combination of trivalent metals selected from the group consisting of aluminum, gallium, chromium, iron, and lanthanum.
  • Both M +2 and M +3 may be mixtures of metals belonging to the respective class.
  • M +2 may be pure nickel or may be both nickel and magnesium, or even nickel-magnesium-cobalt
  • M +3 may be solely aluminum or a mixture of aluminum and chromium, or even a mixture of three trivalent metals such as aluminum, chromium, and gallium.
  • a q is an anion, most usually carbonate although other anions may be employed equivalently, especially anions such as nitrate, sulfate, chloride, bromide, hydroxide, and chromate.
  • M +2 is magnesium
  • M +3 is aluminum
  • A is carbonate corresponds to the hydrotalcite series.
  • the (M +2 x O)(M +3 y O)OH y solid solution has a surface area at least 150 m 2 /g, more preferably at least 200 m 2 /g and it is even more preferable that it be in the range from 300 to 350 m 2 /g.
  • the ratio x/y of the divalent and trivalent metals can vary between 2 and 20, with the ratios of 2 to 10 being preferred.
  • Preparation of suitable basic metal-oxide supports starts with a precursor gel which is prepared at a temperature not exceeding 10°C, and preferably is prepared in the temperature interval between 0 and 5°C.
  • the crystallization time is kept short, on the order of an hour or two at 65°C, to afford layered double hydroxides whose calcination leads to materials of unusual hydrothermal stability.
  • Calcination of the layered double hydroxide is effected at temperatures between 400 and 750°C. Unusual stability and homogeneity is evidenced by the fact that spinel formation is not seen until calcination temperatures of 800°C, whereas the spinel phase begins to appear in prior-art hydrotalcite-type layered double hydroxides at a calcination temperature of 600°C.
  • the catalyst favorably is substantially free of microcrystalline porous material, i.e., a molecular sieve, and in particular is substantially zeolite-free.
  • the ring-cleavage catalyst contains a non-acidic large-pore molecular sieve, an alkali-metal component and a platinum-group metal component.
  • the molecular sieve of this alternative embodiment be non-acidic, as acidity in the sieve lowers the selectivity for ring cleavage of the finished catalyst.
  • the sieve has substantially all of its cationic exchange sites occupied by nor hydrogen species.
  • the cations occupying the exchangeable cation sites will comprise one or more of the alkali metals, although other cationic species may be present.
  • An especially preferred nonacidic large-pore molecular sieve is potassium-form L-zeolite.
  • the large-pore molecular sieve is composited with a binder in order to provide a convenient form for use in the catalyst of the present invention.
  • a binder any refractory inorganic oxide binder is suitable.
  • One or more of silica, alumina or magnesia are preferred binder materials of the present invention.
  • Amorphous silica is especially preferred, and excellent results are obtained when using a synthetic white silica powder precipitated as ultra-fine spherical particles from a water solution.
  • the silica binder preferably is nonacidic, contains less than 0.3 mass % sulfate salts, and has a BET surface area of from 120 to 160 m 2 /g.
  • the large-pore molecular sieve and binder may be composited to form the desired catalyst shape by any method known in the art.
  • the preferred potassium-form L-zeolite and amorphous silica may be commingled as a uniform powder blend prior to introduction of a peptizing agent.
  • An aqueous solution comprising sodium hydroxide is added to form an extrudable dough.
  • the dough preferably will have a moisture content of from 30 to 50 mass % in order to form extrudates having acceptable integrity to withstand direct calcination.
  • the resulting dough is extruded through a suitably shaped and sized die to form extrudate particles, which are dried and calcined by known methods.
  • spherical particles may be formed by methods described hereinabove for the inorganic-oxide ring-cleavage catalyst.
  • An alkali-metal component is an optional constituent of the sieve-containing ring-cleavage catalyst.
  • One or more of the alkali metals including lithium, sodium, potassium, rubidium, cesium and mixtures thereof, may be used, with potassium being preferred.
  • the alkali metal optimally will occupy essentially all of the cationic exchangeable sites of the non-acidic large-pore molecular sieve. Surface-deposited alkali metal also may be present as described in US-A-4619906.
  • the platinum-group metal component comprising one or more of a platinum, palladium, rhodium, ruthenium, iridium or osmium component with a platinum component being preferred, is another essential feature of the ring-cleavage catalysts.
  • This metal component may exist within the catalyst as a compound such as the oxide, sulfide, halide, or oxyhalide, in chemical combination with one or more other ingredients of the catalytic composite, or as an elemental metal. Best results are obtained when substantially all of the metal exists in the catalytic composite in a reduced state.
  • the platinum-group metal component is preferably incorporated by impregnation of the support and generally comprises from about 0.05 to 5 mass % of the catalytic composite, preferably 0.05 to 2 mass %, calculated on an elemental basis.
  • the ring-cleavage catalyst may contain supplemental metal components known to modify the effect of the preferred platinum component.
  • metal modifiers may include Group IVA(14) metals, other Group VIII(8-10) metals, rhenium, indium, gallium, bismuth, zinc, uranium, dysprosium, thallium and mixtures thereof.
  • One or more of rhenium, germanium, tin, lead, gallium, indium and bismuth are preferred modifier metals.
  • Catalytically effective amounts of such metal modifiers may be incorporated into the catalyst by any means known in the art.
  • the final ring-cleavage catalyst generally will be dried at a temperature of from 100° to 320°C for 0.5 to 24 hours, followed by oxidation at a temperature of 300° to 550°C in an air atmosphere which preferably contains a chlorine component for 0.5 to 10 hours.
  • the oxidized catalyst is subjected to a substantially water-free reduction step at a temperature of about 300° to 550°C for 0.5 to 10 hours or more.
  • the duration of the reduction step should be only as long as necessary to reduce the platinum, in order to avoid pre-deactivation of the catalyst, and may be performed in-situ as part of the plant startup if a dry atmosphere is maintained.
  • the above catalysts have been found to provide satisfactory cleavage of rings in a naphtha feedstock at conditions including temperatures within the range of from about 100° to 550°C and preferably 200° to 450°C, with higher temperatures being more appropriate for feedstocks with higher cyclics contents and lower temperatures favoring saturation of aromatic compounds in the feed.
  • Operating pressures range from about 100 kPa to 10 MPa absolute, preferably between about 0.5 and 4 MPa.
  • Hydrogen to hydrocarbon molar ratios relative to the feedstock are in the range of about 0.1 to 100, preferably between about 0.5 and 10.
  • Liquid hourly space velocities (LHSV) range from about 0.1 to 30, and optimally are in the range of about 0.5 to 10.
  • the paraffinic intermediate from the ring-cleavage zone has a low cyclics content, relative to the naphtha feedstock. At least about 50%, preferably at least about 60%, and more advantageously about 70% or more of the naphthenes in the feedstock are converted in the ring-cleavage zone by selective ring opening according to the invention to form principally paraffins having the same carbon number as the converted naphthenes. Ring-cleavage selectivity, expressed as mass % yield of paraffins having the same carbon number as the naphthenes converted, is at least about 90% and preferably about 95% or more. Aromatics in the feedstock which have been saturated in the ring-cleavage zone to form naphthenes are converted to paraffins to a similar extent.
  • the aromatics content generally is reduced about 90% or more relative to that of the naphtha feedstock; usually the aromatics content will be less than about 0.1 mass%, and often in the region of about 100 mass ppm or less, although such low levels are not critical to the utility of the process combination.
  • the intermediate preferably is transferred between zones without separation of hydrogen or light hydrocarbons.
  • the exothermic saturation reaction provides a heated, paraffinic intermediate to the isomerization zone which generally requires no further heating to effect the required isomerization temperature.
  • a cooler or other heat exchanger between the ring-cleavage zone and isomerization zone may be appropriate for temperature flexibility or for the startup of the process combination.
  • Contacting within the ring-cleavage and isomerization zones may be effected using the catalyst in a fixed-bed system, a moving-bed system, a fluidized-bed system, or in a batch-type operation.
  • a fixed-bed system is preferred.
  • the reactants may be contacted with the bed of catalyst particles in either upward, downward, or radial-flow fashion.
  • the reactants may be in the liquid phase, a mixed liquid-vapor phase, or a vapor phase when contacted with the catalyst particles, with excellent results being obtained by application of the present invention to a primarily liquid-phase operation.
  • the isomerization zone may be in a single reactor or in two or more separate reactors with suitable means therebetween to insure that the desired isomerization temperature is maintained at the entrance to each zone. Two or more reactors in sequence are preferred to enable improved isomerization through control of individual reactor temperatures and for partial catalyst replacement without a process shutdown.
  • Isomerization conditions in the isomerization zone include reactor temperatures usually ranging from 40° to 250°C. Lower reaction temperatures are generally preferred in order to favor equilibrium mixtures having the highest concentration of high-octane highly branched isoalkanes and to minimize cracking of the feed to lighter hydrocarbons. Temperatures in the range of from 40° to 150°C are preferred in the present invention.
  • Reactor operating pressures generally range from about 100 kPa to 10 MPa absolute, preferably between about 0.5 and 4 MPa.
  • Liquid hourly space velocities range from about 0.2 to about 15 volumes of isomerizable hydrocarbon feed per hour per volume of catalyst, with a range of about 0.5 to 5 hr -1 being preferred.
  • Hydrogen is admixed with or remains with the paraffinic intermediate to the isomerization zone to provide a mole ratio of hydrogen to hydrocarbon feed of 0.01 to 5.
  • the hydrogen may be supplied totally from outside the process or supplemented by hydrogen recycled to the feed after separation from reactor effluent.
  • Light hydrocarbons and small amounts of inerts such as nitrogen and argon may be present in the hydrogen.
  • Water should be removed from hydrogen supplied from outside the process, preferably by an adsorption system as is known in the art.
  • the hydrogen to hydrocarbon mol ratio in the reactor effluent is equal to or less than 0.05, generally obviating the need to recycle hydrogen from the reactor effluent to the feed.
  • Water and sulfur are catalyst poisons especially for the chlorided platinum-alumina catalyst composition described hereinbelow. Water can act to permanently deactivate the catalyst by removing high-activity chloride from the catalyst, and sulfur temporarily deactivates the catalyst by platinum poisoning. Feedstock hydrotreating as described hereinabove usually reduces water-generating oxygenates to the required 0.1 ppm or less and sulfur to 0.5 ppm or less. Other means such as adsorption systems for the removal of sulfur and water from hydrocarbon streams are well known to those skilled in the art.
  • Any catalyst known in the art to be suitable for the isomerization of paraffin-rich hydrocarbon streams may be used as an isomerization catalyst in the isomerization zone.
  • One suitable isomerization catalyst comprises a platinum-group metal, hydrogen-form crystalline aluminosilicate and a refractory inorganic oxide, and the composition preferably has a surface area of at least 580 m 2 /g.
  • the preferred noble metal is platinum which is present in an amount of from 0.01 to 5 mass % of the composition, and optimally from 0.15 to 0.5 mass %.
  • Catalytically effective amounts of one or more promoter metals preferably selected from Groups VIB(6), VIII(8-10), IB(11), IIB(12), IVA(14), rhenium, iron, cobalt, nickel, gallium and indium also may be present.
  • the crystalline aluminosilicate may be synthetic or naturally occurring, and preferably is selected from the group consisting of FAU, LTL, MAZ and MOR with mordenite having a silica-to-alumina ratio of from 16:1 to 60:1 being especially preferred.
  • the crystalline aluminosilicate generally comprises from about 50 to 99.5 mass % of the composition, with the balance being the refractory inorganic oxide.
  • a preferred isomerization catalyst composition comprises one or more platinum-group metals, a halogen, and an inorganic-oxide binder.
  • the catalyst contains a Friedel-Crafts metal halide, with aluminum chloride being especially preferred.
  • the optimal platinum-group metal is platinum which is present in an amount of from 0.1 to 5 mass %.
  • the inorganic oxide preferably comprises alumina, with one or more of gamma-alumina and eta-alumina providing best results.
  • the carrier material is in the form of a calcined cylindrical extrudate.
  • the composition may also contain an organic polyhalo component, with carbon tetrachloride being preferred, and the total chloride content is from 2 to 15 mass %.
  • An organic-chloride promoter preferably carbon tetrachloride, is added during operation to maintain a concentration of 30 to 300 mass ppm of promoter in the combined feed.
  • An organic-chloride promoter preferably carbon tetrachloride
  • Other details and alternatives of preparation steps and operation of the preferred isomerization catalyst are as disclosed in US-A-2999074 and US-A-3031419.
  • the isomerization zone generally comprises a separation section, optimally comprising one or more fractional distillation columns having associated appurtenances and separating lighter components from an isoparaffin-rich product.
  • a fractionator may separate an isoparaffin concentrate from a cyclics concentrate with the latter being recycled to the ring-cleavage zone.
  • the isoparaffin-rich product and/or the isoparaffin concentrate are blended into finished gasoline along with other gasoline components from refinery processing including but not limited to one or more of butanes, butenes, pentanes, naphtha, catalytic reformate, isomerate, alkylate, polymer, aromatic extract, heavy aromatics; gasoline from catalytic cracking, hydrocracking, thermal cracking, thermal reforming, steam pyrolysis and coking; oxygenates such as methanol, ethanol, propanol, isopropanol, TBA, SBA, MTBE, ETBE, MTAE and higher alcohols and ethers; and small amounts of additives to promote gasoline stability and uniformity, avoid corrosion and weather problems, maintain a clean engine and improve driveability.
  • refinery processing including but not limited to one or more of butanes, butenes, pentanes, naphtha, catalytic reformate, isomerate, alkylate, polymer, aromatic extract, heavy aromatics; gasoline from catalytic cracking
  • Example 1 The acidic catalysts described in Example 1 were microreactor-tested for efficiency in ring cleavage.
  • the feed was substantially pure methylcyclopentane, and the tests were performed at a temperature of 350°C, a hydrogen/hydrocarbon mol ratio of 60, and a liquid hourly space velocity of 2.0.
  • ring-cleavage selectivity was measured as mass % yield of paraffins, dehydrogenation selectivity as mass % aromatics, and cracking selectivity as mass % C 1 -C 5 hydrocarbons: Catalyst Conversion Cleavage Dehydro.
  • a catalyst was prepared by the impregnation of hydrotalcite to compare ring-cleavage performance against acidic catalysts of the prior art.
  • a 2 L, 3-necked round bottomed flask was equipped with an addition funnel, a thermometer, a mechanical stirrer, and a heating mantle. To this flask was added a solution containing 610 g of water, 60 g of Na 2 CO 3 •H 2 O and 71 g of NaOH and the contents were cooled to, 5° C.
  • the addition funnel was charged with a solution of 345 g water, 77 g Mg(NO 3 ) 2 •6H 2 O and 75 g Al(NO 3 ) 3 •9H 2 O and this solution was added over a period of 4 hours. The solution temperature was maintained at, 5° C. throughout the addition and the resulting slurry wa stirred for 1 hour at, 5° C.
  • Catalyst X was prepared using organic Pt impregnation.
  • the aforementioned solid solution in an amount of 42.6 g was impregnated with 1.246 g of Pt-ethylhexanoate in 50 cc acetone. After mixing support and solution for 3 hours the excess of acetone was evaporated and catalyst was dried at 200 C in 3600 cc/hr air for 3 hours and reduced with H 2 for 2 hours.
  • the finished catalyst contained 0.75% Pt.
  • Two nonacidic aluminas of invention were prepared by the addition of K to compare ring-cleavage performance with acidic catalysts of the prior art.
  • Catalyst Y was prepared by the impregnation of 77.4 g gamma alumina with 120 cc water solution of 1.24 g Pt(NH 3 ) 4 Cl, as above 3.05 g KNO 3 and 2.2 g HNO 3 in the rotary evaporator. After 2 hours of cold roll and excess of solution was evaporated for 2 hours and catalyst calcined and reduced as X-1 in Example 3. The finished catalyst contained 0.9% Pt and 1.5%K and had a B-E-T surface area of 180m 2 /g.
  • Catalyst Z was prepared following the same procedure as catalyst Y but 59 g of theta alumina were impregnated with 0.525 g Pt(NH 3 ) 4 C 12 and 0.437 g of KNO 3 .
  • the finished catalyst contained 0.9%Pt and 0.79%K and had a B-E-T surface area of 80 m 2 /g.
  • Catalysts X, Y and Z of the invention were tested for efficiency in ring cleavage in the manner described in Example 2 for acidic catalysts of the prior art.
  • the feed was substantially pure methylcyclopentane, and the tests were performed at a temperature of 350°C, a hydrogen/hydrocarbon mol ratio of 60, and a liquid hourly space velocity of 2.0.
  • ring-cleavage selectivity was measured as mass % yield of paraffins having the same carbon number, dehydrogenation selectivity as mass % aromatics, and cracking selectivity as mass % C 1 -C 5 hydrocarbons: Catalyst Conversion Cleavage Dehydro.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19950117015 1995-10-28 1995-10-28 Two step process for upgrading of cyclic naphthas Expired - Lifetime EP0770666B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES95117015T ES2158026T3 (es) 1995-10-28 1995-10-28 Procedimiento en dos etapas para la mejora de naftas ciclicas.
DE1995621319 DE69521319T2 (de) 1995-10-28 1995-10-28 Zweistufiges Verfahren zur Verbesserung von zyklischem Naphtha
EP19950117015 EP0770666B1 (en) 1995-10-28 1995-10-28 Two step process for upgrading of cyclic naphthas
DK95117015T DK0770666T3 (da) 1995-10-28 1995-10-28 Totrinsproces for opgradering af cykliske naphthaer

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Application Number Priority Date Filing Date Title
EP19950117015 EP0770666B1 (en) 1995-10-28 1995-10-28 Two step process for upgrading of cyclic naphthas

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EP0770666A1 EP0770666A1 (en) 1997-05-02
EP0770666B1 true EP0770666B1 (en) 2001-06-13

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CA2541051C (en) * 2005-09-20 2013-04-02 Nova Chemicals Corporation Aromatic saturation and ring opening process
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JP2024514945A (ja) * 2021-04-23 2024-04-03 中国石油化工股▲ふん▼有限公司 軽質芳香族炭化水素の調製方法
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ES2158026T3 (es) 2001-09-01
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DE69521319D1 (de) 2001-07-19
EP0770666A1 (en) 1997-05-02

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