EP0067014B1 - Katalytischer Reformierprozess - Google Patents

Katalytischer Reformierprozess Download PDF

Info

Publication number
EP0067014B1
EP0067014B1 EP19820302733 EP82302733A EP0067014B1 EP 0067014 B1 EP0067014 B1 EP 0067014B1 EP 19820302733 EP19820302733 EP 19820302733 EP 82302733 A EP82302733 A EP 82302733A EP 0067014 B1 EP0067014 B1 EP 0067014B1
Authority
EP
European Patent Office
Prior art keywords
catalyst
reactor
rhenium
platinum
naphtha
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
Application number
EP19820302733
Other languages
English (en)
French (fr)
Other versions
EP0067014A1 (de
Inventor
George Alexander Swan
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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 Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0067014A1 publication Critical patent/EP0067014A1/de
Application granted granted Critical
Publication of EP0067014B1 publication Critical patent/EP0067014B1/de
Expired legal-status Critical Current

Links

Images

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

Definitions

  • Catalytic reforming is a well-established industrial process employed by the petroleum industry for improving the octane quality of naphthas or straight run gasolines.
  • a multi-functional catalyst is employed which contains a metal hydrogenation-dehydrogenation (hydrogen transfer) component, or components, substantially atomically dispersed upon the surface of a porous, inorganic oxide support, notably alumina.
  • Noble metal catalysts notably of the platinum type, are currently employed, reforming being defined as the total effect of the molecular changes, or hydrocarbon reactions, produced by dehydrogenation of cyclohexanes and dehydroisomerization of alkylcyclopentanes to yield aromatics; dehydrogenation of paraffins to yield olefins; dehydrocyclization of paraffins and olefins to yield aromatics; isomerization of n-paraffins; isomerization of alkylcycloparaffins to yield cyclohexanes; isomerization of substituted aromatics; and hydrocracking of paraffins which produces gas, and inevitably coke, the latter being deposited on the catalyst.
  • Platinum has been widely commercially used in recent years in the production of reforming catalysts, and platinum-on-alumina catalysts have been commercially employed in refineries for the last few decades. In the last decade, additional metallic components have been added to platinum as promotors to further improve the activity or selectivity, or both, of the basic platinum catalyst e.g., iridium, rhenium, tin, and the like. Some catalysts possess superior activity, or selectivity, or both, as contrasted with other catalysts.
  • Platinum-rhenium catalysts by way of example possess admirable selectivity as contrasted with platinum catalysts, selectivity being defined as the ability of the catalyst to produce high yields of C 5 + liquid products with concurrent low production of normally gaseous hydrocarbons, i.e., methane and other gaseous hydrocarbons, and coke.
  • a series of reactors constitute the heart of the reforming unit.
  • Each reforming reactor is generally provided with fixed beds of the catalyst which receive upflow or downflow feed, and each is provided with a heater, because the reactions which take place are endothermic.
  • a naphtha feed, with hydrogen, or hydrogen recycle gas is concurrently passed through a preheat furnace and reactor, and then in sequence through subsequent interstage heaters and reactors of the series.
  • the product from the last reactor is separated into a liquid fraction, and a vaporous effluent.
  • the latter is a gas rich in hydrogen, and usually contains small amounts of normally gaseous hydrocarbons, from which hydrogen is separated from the Cs liquid product and recycled to the process to minimize coke production.
  • the activity of the catalyst gradually declines due to buildup of coke. Coke formation is believed to result from the deposition of coke precursors such as anthracene, coronene, ovalene and other condensed ring aromatic molecules on the catalyst, these polymerizing to form coke. During operation, the temperature of the process is gradually raised to compensate for the activity loss caused by the coke deposition. Eventually, however, economics dictate the necessity of reactivating the catalyst. Consequently, in all processes of this type the catalyst must necessarily be periodically regenerated by burning the coke off the catalyst at controlled conditions, this constituting an initial phase of catalyst reactivation.
  • the reactors are individually isolated, or in effect swung out of line by various manifolding arrangements, motor operated valving and the like.
  • the catalyst is regenerated to remove the coke deposits, and then reactivated while the other reactors of the series remain on stream.
  • a "swing reactor” temporarily replaces a reactor which is removed from the series for regeneration and reactivation of the catalyst, until it is put back in series.
  • a response to this demand embodies a process described in said published U.K. Application 2060682A, wherein, in a series of reforming zones, or reactors, each of which contains a bed, or beds of catalysts, the catalyst in the leading reforming zones is constituted of supported platinum and a relatively low concentration of rhenium, and in the last reforming zone, or reactor of the series, the catalyst is constituted of platinum and a relatively high concentration of rhenium.
  • the amount of rhenium relative to the platinum in the catalyst contained in the last reforming zone, or reactor is in fact present in an atomic ratio of rhenium:platinum of at least 1.5:1 and higher, and preferably the atomic ratio of rhenium:platinum ranges at least 2:1, and higher, and more preferably from 2:1 to 3:1.
  • the leading reforming zones, or reactors of the series are provided with platinum-rhenium catalysts wherein the atomic ratio of the rhenium-platinum ranges from 0.1:1 to 1:1, preferably from 0.3:1 to 1:1.
  • the beds of catalyst are contacted with a hydrocarbon or naphtha feed, and hydrogen, at reforming conditions to produce a hydrocarbon, or naphtha product of improved octane, and the product is withdrawn.
  • the amount of coke produced in an operating run increases progressively from a leading reactor to a subsequent reactor, or from the first reactor to the last, or tail reactor of the series as a consequence of the different types of reactions that predominate in the several different reactors.
  • the metal site, or hydrogenation-dehydrogenation component of the catalyst plays a dominant role and the predominant reaction involves the dehydrogenation of naphthenes to aromatics. This reaction proceeds at relatively low temperature, and the coke formation is relatively low.
  • the acid site plays an important role in isomerizing paraffins and naphthenes, and the additional naphthenes are dehydrogenated to aromatics as in the first reactor.
  • the temperature is maintained higher than in the first reactor, and the temperature in the third reactor is maintained higher than that of the second reactor of the series. Carbon formation is higher in these reactors than in the first reactor of the series, and coke is higher in the third reactor than in the second reactor of the series.
  • the chief reaction in the last, or tail reactor of the series involves dehydrocyclization of paraffins, and the highest temperature is employed in this reactor. Coke formation is highest in this reactor, and the reaction is often the most difficult to control. It is also generally known that these increased levels of coke in the several reactors of the series causes considerable deactivation of the catalysts.
  • the catalysts within the series of reactors are progressively staged with respect to the rhenium concentration, the rhenium concentration being increased from the first to the last reactor of the series such that the rhenium content of the platinum-rhenium catalysts is varied significantly to counteract the normal effects of coking.
  • cyclic reforming typically three or four reactors are arranged in series, and a swing reactor is manifolded in the unit such that it can occupy any position in the reactor train as reactors are taken out of service and the catalyst regenerated, and reactivated.
  • a swing reactor is manifolded in the unit such that it can occupy any position in the reactor train as reactors are taken out of service and the catalyst regenerated, and reactivated.
  • the swing reactor spends less than about twenty-five percent of the time in the first two reactor positions of the series, while in the remaining period the swing reactor occupies either the third or last reactor position.
  • the last reactor of the series remains on oil about seventy percent of the time.
  • the present invention provides a process for a process for reforming naphtha, with hydrogen, in a cyclic reforming unit comprised of a plurality of serially connected on-stream platinum-rhenium catalyst-containing reactors, inclusive of one or more lead reactors, a tail reactor and a swing reactor which can be substituted for any one of the on-stream reactors while the latter is off-stream for regeneration and reactivation of the catalyst, the catalyst of the tail reactor containing a major concentration of rhenium relative to the concentration of the platinum, as contrasted with the concentrations of rhenium and platinum contained in the lead reactors, the atomic ratio of rhenium:platinum in the tail reactor being at least 1.5:1, and the catalyst of the lead reactors containing a minor concentration of rhenium or no more than an equal amount of rhenium, relative to the platinum, the naphtha flowing in sequence from one reactor of the series to another and contacting the catalyst at reforming conditions in the presence of hydrogen, characterized in that the first catalyst contacted
  • the amount of rhenium relative to the platinum in the last reforming reactor, and in the last (e.g. lower) bed of the swing reactor is higher than an atomic ratio of 1.5:1, more preferably from 2:1 to 3: 1.
  • the amount of rhenium relative to the platinum in the initial and intermediate onstream reactors of the series, and the first (e.g. upper) bed of the swing reactor are provided with platinum-rhenium catalyst wherein the atomic ratio of rhenium:platinum may range from 0.01:1 to 1:1, e.g. from 0.1:1 to 1:1, and preferably from 0.3:1 to 1:1, most preferably from 0.5:1 to 1:1.
  • the beds of catalyst in the several reactors, inclusive of the swing reactor are serially contacted with a hydrocarbon or naphtha feed, and hydrogen, at reforming conditions, the feed flowing from one reactor of the series to the rest, serially through the first (e.g. upper) and last (e.g. lower) beds of the swing reactor, to produce a hydrocarbon, or naphtha product of improved octane, and the product is withdrawn.
  • Staged system credits in selectivity, catalyst activity and catalyst activity maintenance are provided by the use of a swing reactor containing an upper fixed bed of platinum-rhenium catalyst having a relatively low concentration of rhenium:platinum, and a lower fixed bed of platinum-rhenium catalyst having a relatively high concentration of rhenium:platinum.
  • the upper bed reactor contains from 50 to 90 percent, preferably from 70 percent to 85 percent of the catalyst, based on the weight of catalyst in the reactor; the balance of the catalyst (50 percent to 10 percent, preferably 30 percent to 15 percent) being contained in the lower bed, or beds, of the reactor.
  • the endotherm is sufficient to minimize cracking reactions in the lower zone of the reactor, thereby suppressing Cs liquid yield loss.
  • the high concentration of rhenium in the lower bed, or beds is beneficial in improving coke tolerance at the elevated temperatures.
  • the Figure depicts, by means of a simplified flow diagram, a preferred cyclic reforming unit inclusive of multiple on-stream reactors, and an alternate or swing reactor inclusive of manifolds for use with catalyst regeneration and reactivation equipment (not shown).
  • a cyclic unit comprised of a multi-reactor system, inclusive of on-stream Reactors A, B, C, D, and a swing Reactor S, and a manifold useful with a facility for periodic regeneration and reactivation of the catalyst of any given reactor, swing Reactor S being manifolded to Reactors A, B, C, D so that it can serve as a substitute reactor for purposes of regeneration and reactivation of the catalyst of a reactor taken off-stream.
  • the several reactors of the series A, B, C, D are arranged so that while one reactor is off-stream for regeneration and reactivation of the catalyst, the swing Reactor S can replace it and provision is also made for regeneration and reactivation of the catalyst of the swing reactor.
  • the on-stream Reactors A, B, C, D each of which is provided with a separate furnace or heater, F AI or reheater F,,, F c , Fp, respectively, are connected in series via an arrangement of connecting process piping and valves so that feed can be passed in seratim through F A A, F B B, F c C, F D D, respectively; or generally similar grouping wherein any of Reactors A, B, C, D are replaced by Reactor S.
  • This arrangement of piping and valves is designated by the numeral 10. Any one of the on-stream Reactors A, B, C, D, respectively, can be substituted by Swing Reactor S as when the catalyst of any one of the former requires regeneration and reactivation.
  • the reactor regeneration sequence is practiced in the order which will optimize the efficiency of the catalyst based on a consideration of the amount of coke deposited on the catalyst of the different reactors during the operation. Coke deposits much more rapidly on the catalyst of Reactors C, D, and S than on the catalyst of Reactors A and B and, accordingly, the catalysts of the former are regenerated and reactivated at greater frequency than the latter.
  • the reactor regeneration sequence is characteristically in the order ACDS/BCDS, i.e., Reactors A, C, D, B, etc., respectively, are substituted in order by another reactor, typically swing Reactor S, and the catalyst thereof regenerated and reactivated while the other four reactors are left on-stream.
  • substantially all or a major portion of the moisture is scrubbed, or adsorbed from the hydrogen recycle gas which is returned to the unit to maintain a dry system.
  • the recycle gas of the stream should be dried sufficiently such that it contains a maximum of about 50 parts, preferably 20 parts, per million parts of water.
  • Reactors A, B and C were each then charged with a portion of Catalyst X.
  • Reactor D, and the lower portion of Reactor S were each then charged with a catalyst, Catalyst Y, similar in all respects to Catalyst X and similarly treated, except that Catalyst Y (dry basis) was of the following composition:
  • the catalyst type charged to each reactor and the fraction of the total catalyst charge, based on the weight of the total catalyst in all reactors, the catalyst regeneration time required for each reactor in its respective position, and the equivalent isothermal temperature (E.I.T.) in each of the runs is given in Table 1.
  • the regeneration in each instance was accomplished by burning the coke from the coked catalyst, initially by burning at 950°F (510°C) by the addition of a gas which contained 0.6 mole percent oxygen; and thereafter the temperature was maintained at 950°F (510°C) while the oxygen concentration in the gas was increased to 6 mole percent.
  • Reactivation in each instance was conducted by the steps of: (a) redispersing the agglomerated metals by contact of the catalyst with a gaseous admixture containing sufficient carbon tetrachloride to decompose in situ and deposit 0.1 wt.% chloride on the catalyst; (b) continuing to add a gaseous mixture containing 6% oxygen for a period of 2 to 4 hours while maintaining temperature of 950°F (510°C); (c) purging with nitrogen to remove essentially all traces of oxygen from the reactor; and (d) reducing the metals of the catalyst of contact with a hydrogen-containing gas at 850°F (454°C).
  • the activation of the catalyst was completed by sulfiding the catalyst of all of Reactors A, B, C, D and S by direct contact with a gaseous admixture of n-butyl mercaptan in hydrogen, sufficient to deposit 0.001-0.1 wt.% sulfur on the catalyst.
  • Table 3 there is tabulated a conventional reactor regeneration sequence ACDS/BCDS, inclusive of starting step "O" (Column 1) wherein all of Reactors A, B, C, and D are on-stream and serially aligned, with swing Reactor S in standby, and eight additional steps, viz. steps 1 through 8, wherein Reactors A, C, D, and B, C, D, are replaced one by one with swing Reactor S.
  • the fourth column of the table shows the time period each reactor remains off-stream for regeneration, and reactivation; a total of 264 hours.
  • the use of the high rhenium platinum-rhenium catalyst in the tail reactor can provide a 15% activity credit and a 1.0% C 5 + liquid volume yield credit as contrasted with an operation which employs a conventional platinum-rhenium catalyst, or platinum-rhenium catalyst which contains an atomic ratio of rhenium:platinum of 1:1 in all of the reactors of the unit.
  • the lower catalyst bed of swing Reactor S of the present invention takes advantage of the endotherm which normally occurs in the bottom portion of a reactor in the A and B positions, this preventing yield loss by cracking such as has been observed with high rhenium platinum-rhenium catalysts employed in lead reactor positions (i.e., swing reactor charged with 100% high rhenium platinum-rhenium catalysts).
  • optimum utilization of rhenium-promoted platinum catalysts is obtained by providing the catalyst of the initial, or first reactor of the series with rhenium in concentration adequate to provide an atomic ratio of rhenium:platinum ranging from 0.1:1 to 0.5:1, preferably from 0.3:1 to 0.5:1.
  • the catalyst of the intermediate reforming zones, as represented by the reactors intermediate between the first and last reactors of the series, and the upper portion of the swing reactor are provided with rhenium in concentration adequate to provide an atomic ratio of rhenium:platinum ranging from 0.5:1 to 1:1, preferably above 0.5:1 to 0.8:1.
  • the last reactor of the series and lower portion of the swing reactor are provided with rhenium in concentration adequate to provide an atomic ratio of rhenium:platinum from 1.5:1 to 3:1, preferably from 2:1 to 3:1.
  • the last reactor of a series, whether the series contains less than three or more than three reactors, and the lower portion of the swing reactor are always provided with a catalyst which contains an atomic ratio of rhenium:platinum of at least 1.5:1 and preferably contains an atomic ratio of rhenium:platinum ranging from 2:1 to 3:1.
  • the catalyst employed in accordance with this invention is necessarily constituted of composite particles which contain, besides a carrier or support material, a hydrogenation-dehydrogenation component, or components, a halide component and, preferably, the catalyst is sulfided.
  • the support material is constituted of a porous, refractory inorganic oxide, particularly alumina.
  • the support can contain, e.g., one or more of alumina, bentonite, clay, diatomaceous earth, zeolite, silica, activated carbon, magnesia, zirconia, thoria, and the like; though the most preferred support is alumina to which, if desired, can be added a suitable amount of other refractory carrier materials such as silica, zirconia, magnesia, titania, etc., usually in a range of 1 to 20 percent, based on the weight of the support.
  • a preferred support for the practice of the present invention is one having a surface area of more than 50 m 2 fg, preferably from 100 to 300 m 2 /g, a bulk density of 0.3 to 1.0 g/ml, preferably 0.4 to 0.8 g/ml, an average pore volume of 0.2 to 1.1 ml/g, preferably 0.3 to 0.8 ml/g, and an average pore diameter of 30 to 300°A (30x10 10 to 300x10 10 m).
  • the metal hydrogenation-dehydrogenation component can be composited with or otherwise intimately associated with the porous inorganic oxide support or carrier by various techniques known to the art such as ion-exchange, co-precipitation with the alumina in the sol or gel form, and the like.
  • the catalyst composite can be formed by adding together suitable reagents such as a salt of platinum and ammonium hydroxide or carbonate, and a salt of aluminum such as aluminum chloride or aluminum sulfate to form aluminum hydroxide.
  • suitable reagents such as a salt of platinum and ammonium hydroxide or carbonate
  • a salt of aluminum such as aluminum chloride or aluminum sulfate
  • the aluminum hydroxide containing the salts of platinum can then be heated, dried, formed into pellets or extruded, and then calcined in nitrogen or other non-agglomerating atmosphere.
  • the metal hydrogenation components can also be added to the catalyst by impregnation, typically via an "incipient wetness" technique which
  • porous refractory inorganic oxides in dry or solvated state are contacted, either alone or admixed, or otherwise incorporated with a metal or metals-containing solution, or solutions, and thereby impregnated by either the "incipient wetness" technique, or a technique embodying absorption from a dilute or concentrated solution, or solutions, with subsequent filtration or evaporation to effect total uptake of the metallic components.
  • Platinum in absolute amount is usually supported on the carrier within the range of from 0.01 to 3 percent, preferably from 0.05 to 1 percent, based on the weight of the catalyst (dry basis).
  • Rhenium, in absolute amount is also usually supported on the carrier in concentration ranging from 0.1 to 3 percent, preferably from 0.5 to 1 percent, based on the weight of the catalyst (dry basis).
  • the absolute concentration of each is preselected to provide the desired atomic ratio of rhenium:platinum for a respective reactor of the unit, as heretofore expressed.
  • the rhenium In the tail reactor, and lower portion of the swing reactor, the rhenium is provided in major amount relative to the platinum whereas, in contrast, in all other reactors and upper portion of the swing reactor the rhenium is provided in minor amount, or no more than about an equal amount, relative to the platinum, based on the atomic weight of these metals, one with respect to the other.
  • essentially any soluble compound can be used, but a soluble compound which can easily be subjected to thermal decomposition and reduction is preferred, for example, inorganic salts such as halide, nitrate, inorganic complex compounds, or organic salts such as the complex salt of acetylacetone, amine salt, and the like.
  • platinum chloride, platinum nitrate, chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum polyamine, platinum acetylacetonate, and the like are preferably used.
  • a promoter metal, or metal other than platinum and rhenium, when employed, is added in concentration ranging from 0.1 to 3 percent, preferably from 0.05 to 1 percent, based on the weight of the catalyst.
  • halogen component to the catalysts, fluorine and chlorine being preferred halogen components.
  • the halogen is contained on the catalyst within the range of 0.1 to 3 percent, preferably within the range of 1 to 1.5 percent, based on the weight of the catalyst.
  • chlorine When using chlorine as a halogen component, it is added to the catalyst within the range of 0.2 to 2 percent, preferably within the range of 1 to 1.5 percent, based on the weight of the catalyst.
  • the introduction of halogen into catalyst can be carried out by any method at any time. It can be added to the catalyst during catalyst preparation, for example, prior to, following or simultaneously with the incorporation of the metal hydrogenation-dehydrogenation component, or components. It can also be introduced by contacting a carrier material in a vapor phase or liquid phase with a halogen compound such as hydrogen fluoride, hydrogen chloride, ammonium chloride, or the like.
  • the catalyst is dried by heating at a temperature above about (80°F) 27°C, preferably between 150°F (66°C) and 300°F (149°C), in the presence of nitrogen or oxygen, or both, in an air stream or under vacuum.
  • the catalyst is calcined at a temperature between 500°F to 1,200°F (260 to 649°C), preferably 500°F to 1,000°F (260 to 538°C), either in the presence of oxygen in an air stream or in the presence of an inert gas such as nitrogen.
  • Sulfur is a highly preferred component of the catalysts, the sulfur content of the catalyst generally ranging to 0.2 percent, preferably from 0.05 percent to 0.15 percent, based on the weight of the catalyst (dry basis).
  • the sulfur can be added to the catalyst by conventional methods, suitably by breakthrough sulfiding of a bed of the catalyst with a sulfur-containing gaseous stream, e.g., hydrogen sulfide in hydrogen, performed at temperatures ranging from 350°F (177°C) to 1,050°F (566°C) and at pressures ranging from 1 to 40 atmospheres for the time necessary to achieve breakthrough, or the desired sulfur level.
  • a sulfur-containing gaseous stream e.g., hydrogen sulfide in hydrogen
  • the feed or charge stock can be a virgin naphtha, cracked naphtha, a naphtha from a coal liquefaction process, a Fischer-Tropsch naphtha, or the like. Such feeds can contain sulfur or nitrogen, or both, at fairly high levels. Typical feeds are those hydrocarbons containing from about 5 to 12 carbon atoms, or more preferably from about 6 to 9 carbon atoms. Naphthas, or petroleum fractions boiling within the range of from 80°F (27°C) to 450°F (232°C), and preferably from 125°F (52°C) to 375°F (191°C), contain hydrocarbons of carbon numbers within these ranges.
  • Typical fractions thus usually contain from 15 to 80 vol.% paraffins, both normal and branched, which fall in the range of C s to C 12 , from 10 to 80 vol.% of naphthenes falling within the range of from C 6 to C 12 .
  • the reforming runs are initiated by adjusting the hydrogen and feed rates, and the temperature and pressure to operating conditions.
  • the run is continued at optimum reforming conditions by adjustment of the major process variables, within the ranges described below:

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)

Claims (8)

1. Verfahren zum Reformieren von Naphtha mit Wasserstoff in einer cyclischen Reformieranlage, die eine Vielzahl von in Serie geschalteten, im Betrieb befindlichen, Platin-Rhenium-Katalysator enthaltenden Reaktoren einschließlich einem oder mehreren Anfangsreaktoren, einem Endreaktor und einem Schwenkreaktor umfaßt, der jeden der im Betrieb befindlichen Reaktoren ersetzen kann, während dieser zwecks Regenerierung und Reaktivierung des Katalysators abgeschaltet ist, bei welchem der Katalysator des Endreaktors eine überwiegende Konzentration an Rhenium im Verhältnis zur Konzentration des Platins im Gegensatz zu den Konzentrationen von Rhenium und Platin in den Anfangsreaktoren aufweist, wobei das Atomverhältnis von Rhenium:Platin im Endreaktor mindestens 1,5:1 beträgt und der Katalysator der Anfangsreaktoren eine geringere Konzentration an Rhenium oder nicht mehr als eine gleich große Menge an Rhenium im Verhältnis zum Platin enthält, und bei welchem das Naphtha nacheinander von einem Reaktor der Serie zum anderen strömt und den Katalysator unter Reformierbedingungen in Gegenwart von Wasserstoff kontaktiert, dadurch gekennzeichnet, daß der erste Katalysator, der vom Naphtha beim Eintreten in den Schwenkreaktor kontaktiert wird, eine geringere Konzentration an Rhenium oder nicht mehr als eine gleich große Menge an Rhenium im Verhältnis zum Platin enthält und der letzte Katalysator, der vom Naphtha vor Verlassen des Schwenkreaktors kontaktiert wird, eine überwiegende Konzentration an Rhenium im Verhältnis zu der Konzentration des Platins aufweist, wobei das Atomverhältnis von Rhenium:Platin desselben mindestens 1,5:1 beträgt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Konzentration oder Menge des Katalysators, der in dem ersten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha enthalten ist und im Verhältnis zum Platin eine verhältnismäßig geringe Konzentration an Rhenium aufweist, im Bereich von 50 bis 90% der Gesamtkatalysatorbeschickung im Schwenkreaktor, bezogen auf das Gewicht des Katalysators in diesem Reaktor, liegt.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Konzentration oder Menge des Katalysators, der in dem letzten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha enthalten ist und der im Verhältnis zum Platin eine verhältnismäßig hohe Konzentration an Rhenium aufweist, im Bereich von 50 bis 10% der Gesamtkatalysatorbeschickung, bezogen auf das Gewicht des Katalysators in diesem Reaktor, liegt.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Atomverhältnis von Rhenium:Platin in dem Katalysator des Endreaktors und in dem letzten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha im Bereich von 2:1 bis 3:1 liegt.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Katalystor des Endreaktors und in dem letzten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha 0,01 bis 3 Gew.% Platin und ausreichend Rhenium enthält, um das angegebene Atomverhältnis von Rhenium:Platin zu liefern.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Katalysator des Endreaktors und in dem letzten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha, bezogen auf das Gewicht des Katalysators, 0,1 bis 3% Halogen enthält.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Katalysator des Endreaktors und in dem letzten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha sulfidiert ist und, bezogen auf das Gewicht des Katalysators, bis zu 0,2% Schwefel enthält.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Atomverhältnis von Rhenium:Platin in dem Katalysator der Anfangsreaktoren und in dem ersten Katalysator des Schwenkreaktors zum Kontaktieren mit dem Naphtha im Bereich von 0,01:1 bis 1:1 liegt.
EP19820302733 1981-06-08 1982-05-27 Katalytischer Reformierprozess Expired EP0067014B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27152881A 1981-06-08 1981-06-08
US271528 1981-06-08

Publications (2)

Publication Number Publication Date
EP0067014A1 EP0067014A1 (de) 1982-12-15
EP0067014B1 true EP0067014B1 (de) 1985-09-25

Family

ID=23035974

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820302733 Expired EP0067014B1 (de) 1981-06-08 1982-05-27 Katalytischer Reformierprozess

Country Status (5)

Country Link
EP (1) EP0067014B1 (de)
JP (1) JPS57212293A (de)
CA (1) CA1189814A (de)
DE (1) DE3266502D1 (de)
MX (1) MX7607E (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ214432A (en) * 1984-12-27 1988-03-30 Mobil Oil Corp A multi-reactor hydrocarbon catalytic conversion process. reactors cyclically operated in a continuous operation during regeneration of the catalyst
FR2966058B1 (fr) * 2010-10-15 2013-11-01 IFP Energies Nouvelles Catalyseur optimise pour le reformage catalytique
CN107365600B (zh) * 2016-05-13 2020-04-21 神华集团有限责任公司 一种非石化类石脑油加氢精制生产催化重整原料的方法及其反应装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174271A (en) * 1977-11-03 1979-11-13 Cosden Technology, Inc. High severity reforming
US4174270A (en) * 1977-11-03 1979-11-13 Cosden Technology, Inc. High severity process for the production of aromatic hydrocarbons
US4166024A (en) * 1978-07-10 1979-08-28 Exxon Research & Engineering Co. Process for suppression of hydrogenolysis and C5+ liquid yield loss in a cyclic reforming unit
US4261811A (en) * 1979-04-06 1981-04-14 Standard Oil Company (Indiana) Reforming with an improved rhenium-containing catalyst

Also Published As

Publication number Publication date
EP0067014A1 (de) 1982-12-15
MX7607E (es) 1990-03-15
CA1189814A (en) 1985-07-02
JPS57212293A (en) 1982-12-27
DE3266502D1 (en) 1985-10-31

Similar Documents

Publication Publication Date Title
US4354925A (en) Catalytic reforming process
US4425222A (en) Catalytic reforming process
US4406775A (en) Catalyst regeneration process
US4348271A (en) Catalytic reforming process
US5368720A (en) Fixed bed/moving bed reforming with high activity, high yield tin modified platinum-iridium catalysts
US5562817A (en) Reforming using a Pt/Re catalyst
US3558479A (en) Low pressure regenerative reforming process for high paraffin feeds
US4440626A (en) Catalytic reforming process
EP0200559B1 (de) Katalytische Reformierungsverfahren
EP0083875B1 (de) Katalytisches Reformierverfahren unter Benutzung eines Platin/Rhenium-Katalysators
US4440627A (en) Catalytic reforming process
EP0067014B1 (de) Katalytischer Reformierprozess
US4613424A (en) Catalytic reforming process
US4342644A (en) Reforming with multimetallic catalysts
US4719005A (en) Catalytic reforming process
US5106809A (en) High activity, high yield tin modified platinum-iridium catalysts, and reforming process utilizing such catalysts
EP0106531B1 (de) Verfahren zur katalytischen Reformierung von Naphtha unter Verwendung eines Rhenium enthaltenden Katalysators
US5066632A (en) Reforming catalyst
US4436612A (en) Catalytic reforming process
US4415435A (en) Catalytic reforming process
US4427533A (en) Catalytic reforming process
US4292204A (en) Reforming with multimetallic catalysts
CA1189813A (en) Catalytic reforming process
US5269907A (en) Process for reforming at low severities with high-activity, high-yield, tin modified platinum-iridium catalysts
EP0127709B1 (de) Verfahren zur Regeneration eines Kohlenwasserstoffreformierungskatalysators

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19830518

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 3266502

Country of ref document: DE

Date of ref document: 19851031

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890322

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19890330

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19890331

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890505

Year of fee payment: 8

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890531

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19900531

BERE Be: lapsed

Owner name: EXXON RESEARCH AND ENGINEERING CY

Effective date: 19900531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19901201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19910201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST