USOO5935415A

United States Patent (19) 11 Patent Number: 5,935,415

Haizmann et al. (45) Date of Patent: *Aug. 10, 1999

54 CONTINUOUS CATALYTIC REFORMING 3,718,578 2/1973 Buss et al. .............................. 208/139

PROCESS WITH IDUAL ZONES 3,873,441 3/1975 Jones ........... ... 208/166
4,125,454 11/1978 Clem et al. ............................... 208/65
75 Inventors: Robert S. Haizmann, Rolling 4,208,397 6/1980 Coates ..................................... 423/651
Meadows; John Y. G. Park, 4,645,586 2/1987 Buss ........ ... 208/65
Naperville; Michael B. Russ, Villa 4,985,132 1/1991 Moser et al..... ... 208/65
Park, all of Ill. 5,190,638 3/1993 Swan, III et al. .. ... 208/65
5,683,573 11/1997 Haizmann et al. ....................... 208/64
73 Assignee: UOP LLC, Des Plaines, Ill.
* Notice: This patent is Subject to a terminal dis- Primary Examiner-Helane Myers
claimer. Attorney, Agent, or Firm Thomas K. McBride; John F.
Spears, Jr.; Richard E. Conser
21 Appl. No.: 08/963,693
57 ABSTRACT
22 Filed: Nov. 4, 1997 57
O O A hydrocarbon feedstock is catalytically reformed in a
Related U.S. Application Data Sequence comprising a continuous-reforming Zone, consist
63 Continuation-in-part of application No. 08/635,857, Apr. 22 ing essentially of a moving-bed catalytic reforming Zone and
1996. Pat No. 5.683573, which is a continuation-in-part of
application No. 08/362,343, Dec. 22, 1994, abandoned.
continuous regeneration of catalyst particles, and a Zeolitic
reforming Zone containing a catalyst comprising a platinum
(51) Int. Cl." .....................................................
52 U.S. CI
c10o 35/06
208/64; 208/63; 208/65
group metal and a nonacidic zeolite. The process combina
tion permits higher Severity, higher aromatics yields and/or
58 Field Of search - - - - - s 208/64 63. 65 increased throughput in the continuous-reforming Zone, thus
-- --- ---------- --- ------------ ----- s s/-1s showing Surprising benefits over prior-art processes, and is

56) References Cited particularly useful in upgrading existing moving-bed

reforming facilities with continuous catalyst regeneration.
U.S. PATENT DOCUMENTS
3,652,231 3/1972 Greenwood et al. ................. 23/288 G 15 Claims, 2 Drawing Sheets
U.S. Patent Aug. 10, 1999 Sheet 1 of 2 5,935,415

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 5,935,415
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CONTINUOUS CATALYTIC REFORMING U.S. Pat. No. 4,645,586 (Buss) teaches contacting a feed
PROCESS WITH IDUAL ZONES with a bifunctional reforming catalyst comprising a metallic
CROSS REFERENCE TO RELATED oxide support and a Group VIII metal followed by a zeolitic
APPLICATIONS reforming catalyst comprising a large-pore Zeolite which
preferably is zeolite L. The deficiencies of the prior art are
This application is a continuation-in-part of prior appli overcome by using the first conventional reforming catalyst
cation Ser. No. 08/635,857, filed Apr. 22, 1996, U.S. Pat. No. to provide a product Stream to the Second, non-acidic,
5,683,573, which is a continuation-in-part of prior applica high-Selectivity catalyst. There is no Suggestion of continu
tion Ser. No. 08/362,343, filed Dec. 22, 1994, abandoned ous reforming in BuSS, however.
Apr. 18, 1996. U.S. Pat. No. 4,985,132 (Moser et al.) teaches a multizone
BACKGROUND OF THE INVENTION catalytic reforming process, with the catalyst of the initial
1. Field of the Invention Zone containing platinum-germanium on a refractory inor
This invention relates to an improved proceSS for the ganic oxide and the terminal catalyst Zone being a moving
conversion of hydrocarbons, and more specifically for the bed System with associated continuous catalyst regeneration.
catalytic reforming of gasoline-range hydrocarbons. 15 However, there is no disclosure of an L-Zeolite component.
2. General Background U.S. Pat. No. 5,190,638 (Swan et al.) teaches reforming in
Continuous catalytic reforming, using a moving bed of a moving-bed continuous-catalyst-regeneration mode to
catalyst to effect reforming and continuously regenerating produce a partially reformed Stream to a Second reforming
the moving bed of catalyst to avoid its deactivation, has Zone preferably using a catalyst having acid functionality at
dominated new reforming-unit construction in recent years. 100-500 psig, but does not disclose the use of a nonacidic
The catalytic reforming of hydrocarbon feedstocks in the Zeolitic catalyst.
gasoline range is practiced in nearly every significant petro U.S. Pat. No. 3,652,231 (Greenwood et al.) teaches regen
leum refinery in the World to produce aromatic intermediates eration and reconditioning of a reforming catalyst in a
for the petro- chemical industry or gasoline components 25
moving column, but does not Suggest two Zones of reform
with high resistance to engine knock. Demand for aromatics ing.
is growing more rapidly than the Supply of feedstocks for SUMMARY OF THE INVENTION
aromatics production. Moreover, increased gasoline upgrad
ing necessitated by environmental restrictions and the rising It is an object of the present invention to provide a
demands of high-performance internal-combustion engines catalytic reforming process which effects an improved prod
are increasing the required knock resistance of the gasoline uct yield structure. A corollary objective is to improve
component as measured by gasoline "octane' number. A aromatics yields and performance of a continuous reforming
catalytic reforming unit within a given refinery, therefore, proceSS.
often must be upgraded in capability in order to meet these This invention is based on the discovery that a combina
increasing aromatics and gasoline-octane needs. Such 35 tion of continuous catalytic reforming and Zeolitic reforming
upgrading as applied to a continuous catalytic reforming shows Surprising improvements in aromatics yields and
process desirably would make efficient use of the existing process utilization relative to the prior art.
reforming and catalyst-regeneration equipment. Abroad embodiment of the present invention is a catalytic
Catalytic reforming generally is applied to a feedstock reforming process combination in which a hydrocarbon
rich in paraffinic and naphthenic hydrocarbons and is 40 feedstock is processed Successively by continuous catalytic
effected through diverse reactions: dehydrogenation of reforming, comprising a moving bed with continuous cata
naphthenes to aromatics, dehydrocyclization of paraffins, lyst regeneration, and in a Zeolitic-reforming Zone contain
isomerization of paraffins and naphthenes, dealkylation of ing a catalyst which comprises a nonacidic Zeolite and a
alkylaromatics, hydrocracking of paraffins to light platinum-group metal. Continuous reforming preferably is
hydrocarbons, and formation of coke which is deposited on 45 effected using a catalyst comprising a refractory inorganic
the catalyst. Increased aromatics and gasoline-octane needs oxide Support, platinum-group metal and halogen, which is
have turned attention to the paraffin-dehydrocyclization at least Semicontinuously regenerated and reconditioned and
reaction, which is less favored thermodynamically and returned to the continuous-reforming reactor. The nonacidic
kinetically in conventional reforming than other aromatiza Zeolite preferably is an L-Zeolite, most preferably
tion reactions. Considerable leverage exists for increasing 50 potassium-form L-Zeolite. The preferred platinum-group
desired product yields from catalytic reforming by promot metal for one or both of the continuous and zeolitic reform
ing the dehydrocyclization reaction over the competing ing catalysts is platinum.
hydrocracking reaction while minimizing the formation of A first effluent from continuous catalytic reforming opti
coke. Continuous catalytic reforming, which can operate at mally is processed in the Zeolitic reforming Zone without
relatively low pressures with high-activity catalyst by con 55 Separation of free hydrogen.
tinuously regenerating catalyst, is effective for dehydrocy In another aspect, the invention comprises adding a
clization. Zeolitic reforming Zone to expand the throughput and/or
The effectiveness of reforming catalysts comprising a enhance product quality of an existing continuous-reforming
non-acidic L-Zeolite and a platinum-group metal for dehy process unit.
drocyclization of paraffins is well known in the art. The use 60 These as well as other objects and embodiments will
of these reforming catalysts to produce aromatics from become apparent from the detailed description of the inven
paraffinic raffinates as well as naphthas has been disclosed. tion.
Nevertheless, this dehydrocyclization technology has been
Slow to be commercialized during the intense and lengthy BRIEF DESCRIPTION OF THE DRAWINGS
development period. The present invention represents a 65 FIG. 1 shows BTX-aromatics yields for the process
novel approach to the complementary use of L-Zeolite combination of the invention in comparison to yields based
technology. on the known art.
 5,935,415
3 4
FIG. 2 compares BTX-aromatics yields for an embodi tacts the Sulfur Sorbent, which advantageously is a Zinc
ment of the invention comprising a Zeolitic-reforming Zone oxide or manganese oxide, to remove HS. Sulfur levels
as a lead Zone to yields from prior-art processes. well below 0.1 mass ppm may be achieved thereby. It is
within the ambit of the present invention that the pretreating
DESCRIPTION OF THE PREFERRED Step be included in the present reforming process.
EMBODIMENTS Each of the continuous-reforming Zone and Zeolitic
To reiterate, a broad embodiment of the present invention reforming Zone contains one or more reactors containing the
is directed to a catalytic reforming proceSS combination in respective catalysts. The feedstock may contact the respec
which a hydrocarbon feedstock is processed Successively by tive catalysts in each of the respective reactors in either
continuous catalytic reforming, comprising a moving bed upflow, downflow, or radial-flow mode. Since the present
with continuous catalyst regeneration, and in a Zeolitic reforming process operates at relatively low pressure, the
reforming Zone containing a catalyst which comprises a low pressure drop in a radial-flow reactor favors the radial
nonacidic Zeolite and a platinum-group metal. An embodi flow mode.
ment of the invention comprises adding a Zeolitic reforming 15
First reforming conditions comprise a pressure, consistent
Zone to expand the capability of an existing continuous with the Zeolitic reforming Zone, of from about 100 kPa to
reforming proceSS unit. 6 MPa (absolute) and preferably from 100 kPa to 1 MPa.
The hydrocarbon feedstock comprises paraffins and (abs). Excellent results have been obtained at operating
naphthenes, and may comprise aromatics and Small amounts pressures of about 450 kPa or less. Free hydrogen, usually
of olefins, boiling within the gasoline range. FeedstockS in a gas containing light hydrocarbons, is combined with the
which may be utilized include Straight-run naphthas, natural feedstock to obtain a mole ratio of from about 0.1 to 10
gasoline, Synthetic naphthas, thermal gasoline, catalytically moles of hydrogen per mole of Cs+ hydrocarbons. Space
cracked gasoline, partially reformed naphthas or raffinates velocity with respect to the volume of first reforming
from extraction of aromatics. The distillation range may be catalyst is from about 0.2 to 10 hr'. Operating temperature
that of a full-range naphtha, having an initial boiling point is from about 400 to 560 C.
25
typically from 40-80 C. and a final boiling point of from The continuous-reforming Zone produces an aromatics
about 160-210 C., or it may represent a narrower range enriched first effluent stream. Most of the naphthenes in the
with a lower final boiling point. Paraffinic feedstocks, such feedstock are converted to aromatics. Paraffins in the feed
as naphthas from Middle East crudes having a final boiling Stock are primarily isomerized, hydrocracked, and
point within the range of about 100-175 C., are advanta dehydrocyclized, with heavier paraffins being converted to a
geously processed since the process effectively dehydrocy greater extent than light paraffins with the latter therefore
clizes paraffins to aromatics. Rafflinates from aromatics predominating in the effluent. The aromatics content of the
extraction, containing principally low-value C-C paraffins Cs+ portion of the effluent is increased by at least 5 mass %
which can be converted to valuable B-T-X aromatics, are relative to the aromatics content of the hydrocarbon feed
favorable alternative hydrocarbon feedstocks. 35 Stock. The composition of the aromatics depends principally
The hydrocarbon feedstock to the present proceSS con on the feedstock composition and operating conditions, and
tains Small amounts of Sulfur compounds, amounting to generally will consist principally of C-C aromatics.
generally less than 10 mass parts per million (ppm) on an During the reforming reaction, catalyst particles become
elemental basis. Preferably the hydrocarbon feedstock has deactivated as a result of mechanisms. Such as the deposition
been prepared from a contaminated feedstock by a conven 40 of coke on the particles to the point that the catalyst is no
tional pretreating Step Such as hydrotreating, hydrorefining longer useful. Such deactivated catalyst must be regenerated
or hydrodeSufurization to convert Such contaminants as and reconditioned before it can be reused in a reforming
Sulfurous, nitrogenous and oxygenated compounds to H2S, proceSS.
NH and HO, respectively, which can be separated from the Continuous reforming permits higher operating Severity
hydrocarbons by fractionation. This conversion preferably 45 by maintaining the high catalyst activity of near-fresh cata
will employ a catalyst known to the art comprising an lyst through regeneration cycles of a few days. A moving
inorganic oxide Support and metals Selected from Groups bed System has the advantage of maintaining production
VIB(6) and VIII(9–10) of the Periodic Table. See Cotton while the catalyst is removed or replaced. Catalyst particles
and Wilkinson, Advanced Inorganic Chemistry, John Wiley pass by gravity through one or more reactors in a moving
& Sons (Fifth Edition, 1988). Alternatively or in addition to 50 bed and is conveyed to a continuous regeneration Zone.
the conventional hydrotreating, the pretreating Step may Continuous catalyst regeneration generally is effected by
comprise contact with Sorbents capable of removing Sulfu passing catalyst particles downwardly by gravity in a
rous and other contaminants. These Sorbents may include moving-bed mode through various treatment Zones in a
but are not limited to Zinc oxide, iron Sponge, high-Surface regeneration vessel. Although movement of catalyst through
area Sodium, high-Surface-area alumina, activated carbons 55 the Zones is often designated as continuous in practice it is
and molecular Sieves, excellent results are obtained with a Semi-continuous in the Sense that relatively Small amounts
nickel-on-alumina Sorbent. Preferably, the pretreating Step of catalyst particles are transferred at closely spaced points
will provide the Zeolitic reforming catalyst with a hydrocar in time. For example, one batch per minute may be with
bon feedstock having low sulfur levels disclosed in the prior drawn from the bottom of a reaction Zone and withdrawal
art as desirable reforming feedstocks, e.g., 1 ppm to 0.1 ppm 60 may take one-half minute; e.g., catalyst particles flow for
(100 ppb). one-half minute in the one-minute period. Since the inven
The pretreating Step may achieve very low Sulfur levels in tory in the reaction and regeneration Zones generally is large
the hydrocarbon feedstock by combining a relatively sulfur in relation to the batch size, the catalyst bed may be
tolerant reforming catalyst with a sulfur sorbent. The sulfur envisaged as moving continuously.
tolerant reforming catalyst contacts the contaminated feed 65 In a continuous-regeneration Zone, catalyst particles are
Stock to convert most of the Sulfur compounds to yield an contacted in a combustion Zone with a hot oxygen
HS-containing effluent. The HS-containing effluent con containing gas Stream to remove coke by oxidation. The
 5,935,415
S 6
catalyst usually next passes to a drying Zone to remove water consumed in the drying Zone can pass upwardly with the flue
by contacting a hot, dry air Stream. Dry catalyst is cooled by gas from the combustion Zone to replace the Oxygen that is
direct contact with an air Stream. Optimally, the catalyst also depleted through the combustion reaction. Contacting the
is halogenated in a halogenation Zone located below the catalyst particles with a gas containing a high concentration
combustion Zone by contact with a gas containing a halogen of oxygen also aids in restoring full activity to the catalyst
component. Finally, catalyst particles are reduced with a particles by raising the oxidation State of the platinum or
hydrogen-containing gas in a reduction Zone to obtain other metals contained thereon. The drying Zone is designed
reconditioned catalyst particles which are conveyed to the to reduce the moisture content of the catalyst particles to no
moving-bed reactor. Details of continuous catalyst more than 0.01 weight fraction based on catalyst before the
regeneration, particularly in connection with a moving-bed catalyst particles leave the Zone.
reforming process, are disclosed below and inter alia in U.S. Following the optional drying Step, the catalyst particles
Pat. Nos. 3,647,680; 3,652,231; 3,692,496; and 4,832,921, preferably are contacted in a separate Zone with a chlorine
all of which are incorporated herein by reference. containing gas to re-disperse the noble metals over the
Spent catalyst particles from the continuous-reforming Surface of the catalyst. Re-dispersion is needed to reverse the
Zone first are contacted in the regeneration Zone with a hot 15
agglomeration of noble metals resulting from exposure to
oxygen-containing gas Stream in order to remove coke high temperatures and Steam in the combustion Zone. Redis
which accumulates on Surfaces of the catalyst during the persion is effected at a temperature of between about
reforming reaction. Coke content of spent catalyst particles 425–600° C., preferably about 510–540. A concentration of
may be as much as 20% of the catalyst weight, but 5–7% is chlorine on the order of 0.01 to 0.2 mol. 9% of the gas and
a more typical amount. Coke comprises primarily carbon the presence of oxygen are highly beneficial to promoting
rapid and complete redispersion of the platinum-group metal
with a relatively Small amount of hydrogen, and is oxidized to obtain redispersed catalyst particles.
to carbon monoxide, carbon dioxide, and water at tempera Regenerated and redispersed catalyst is reduced to change
tures of about 450–550° C. which may reach 600° C. in the noble metals on the catalyst to an elemental State through
localized regions. Oxygen for the combustion of coke enters contact with a hydrogen-rich reduction gas before being
a combustion Section of the regeneration Zone in a recycle 25 used for catalytic purposes. Although reduction of the oxi
gas containing usually about 0.5 to 1.5% oxygen by Volume. dized catalyst is an essential Step in most reforming
Flue gas made up of carbon monoxide, carbon dioxide, operations, the Step is usually performed just ahead or within
water, unreacted oxygen, chlorine, hydrochloric acid, the reaction Zone and is not generally considered a part of
nitrous oxides, Sulfur oxides and nitrogen is collected from the apparatus within the regeneration Zone. Reduction of the
the combustion Section, with a portion being withdrawn highly oxidized catalyst with a relatively pure hydrogen
from the regeneration Zone as flue gas. The remainder is reduction gas at a temperature of about 450-550° C., pref
combined with a Small amount of oxygen-containing erably about 480-510 C., to provide a reconditioned cata
makeup gas, typically air in an amount of roughly 3% of the lyst.
total gas, to replenish consumed oxygen and returned to the During lined-out operation of the continuous-reforming
combustion Section as recycle gas. The arrangement of a 35 Zone, most of the catalyst Supplied to the Zone is a first
typical combustion section may be seen in U.S. Pat. No. reforming catalyst which has been regenerated and recon
3,652,231. ditioned as described above. A portion of the catalyst to the
AS catalyst particles move downward through the com reforming Zone may be first reforming catalyst Supplied as
bustion Section with concomitant removal of coke, a “break makeup to overcome losses to deactivation and fines, par
through' point is reached typically about halfway through ticularly during reforming-proceSS Startup, but these quan
40
the Section where less than all of the oxygen delivered is tities are Small, usually less than about 0.1%, per regenera
tion cycle. The first reforming catalyst is a dual-function
consumed. It is known in the art that the present reforming composite containing a metallic hydrogenation
catalyst particles have a large Surface area associated with a dehydrogenation, preferably a platinum-group metal
multiplicity of pores. When the catalyst particles reach the component, on a refractory Support which preferably is an
breakthrough point in the bed, the coke remaining on the 45 inorganic oxide which provides acid Sites for cracking and
Surface of the particles is deep within the pores and therefore isomerization. The first reforming catalyst effects dehydro
the oxidation reaction occurs at a much slower rate. genation of naphthenes contained in the feedstock as well as
Water in the makeup gas and from the combustion Step is isomerization, cracking and dehydrocyclization.
removed in the Small amount of vented flue gas, and The refractory Support of the first reforming catalyst
therefore builds to an equilibrium level in the recycle-gas 50 should be a porous, adsorptive, high-Surface-area material
loop. The water concentration in the recycle loop optionally which is uniform in composition without composition gra
may be lowered by drying the air that made up the makeup dients of the species inherent to its composition. Within the
gas, installing a drier for the gas circulating in the recycle Scope of the present invention are refractory Support con
gas loop or venting a larger amount of flue gas from the taining one or more of: (1) refractory inorganic oxides Such
recycle gas Stream to lower the water equilibrium in the 55 as alumina, Silica, titania, magnesia, Zirconia, chromia,
recycle gas loop. thoria, boria or mixtures thereof; (2) Synthetically prepared
Optionally, catalyst particles from the combustion Zone or naturally occurring clays and Silicates, which may be
pass directly into a drying Zone wherein water is evaporated acid-treated; (3) crystalline Zeolitic aluminosilicates, either
from the Surface and pores of the particles by contact with naturally occurring or Synthetically prepared Such as FAU,
a heated gas Stream. The gas Stream usually is heated to 60 MEL, MFI, MOR, MTW (IUPAC Commission on Zeolite
about 425-600 C. and optionally pre-dried before heating Nomenclature), in hydrogen form or in a form which has
to increase the amount of water that can be absorbed. been exchanged with metal cations; (4) Spinels Such as
Preferably the drying gas Stream contain oxygen, more MgAl-O, FeAl-O, ZnAl-O, CaAl2O, and (5) combina
preferably with an oxygen content about or in excess of that tions of materials from one or more of these groups. The
of air, So that any final residual burning of coke from the 65 preferred refractory Support for the first reforming catalyst is
inner pores of catalyst particles may be accomplished in the alumina, with gamma- or eta-alumina being particularly
drying Zone and So that any exceSS oxygen that is not preferred.
 5,935,415
7 8
The alumina powder may be formed into any shape or tially waterfree reduction step at a temperature of about 300
form of carrier material known to those skilled in the art to 550° C. for 0.5 to 10 hours or more. Further details of the
Such as Spheres, extrudates, rods, pills, pellets, tablets or preparation and activation of embodiments of the first
granules. Spherical particles may be formed by converting reforming catalyst are disclosed in U.S. Pat. No. 4,677,094
the alumina powder into alumina Sol by reaction with (Moser et al.), which is incorporated into this specification
Suitable peptizing acid and water and dropping a mixture of by reference thereto.
the resulting Sol and gelling agent into an oil bath to form The Zeolitic catalyst is contained in a fixed-bed reactor or
Spherical particles of an alumina gel, followed by known in a moving-bed reactor whereby catalyst may be continu
aging, drying and calcination Steps. The extrudate form is ously withdrawn and added. These alternatives are associ
preferably prepared by mixing the alumina powder with ated with catalyst-regeneration options known to those of
water and Suitable peptizing agents, Such as nitric acid, ordinary skill in the art, Such as: (1) a Semiregenerative unit
acetic acid, aluminum nitrate and like materials, to form an containing fixed-bed reactors maintains operating Severity
extrudable dough having a loss on ignition (LOI) at 500° C. by increasing temperature, eventually shutting the unit down
of about 45 to 65 mass %. The resulting dough is extruded for catalyst regeneration and reactivation; (2) a Swing
through a Suitably shaped and sized die to form extrudate 15 reactor unit, in which individual fixed-bed reactors are
particles, which are dried and calcined by known methods. Serially isolated by manifolding arrangements as the catalyst
Alternatively, Spherical particles can be formed from the become deactivated and the catalyst in the isolated reactor is
extrudates by rolling the extrudate particles on a spinning regenerated and reactivated while the other reactors remain
disk. on-stream; (3) continuous regeneration of catalyst with
The particles are usually Spheroidal and have a diameter drawn from a moving-bed reactor, with reactivation and
of from about /16th to about /sth inch (1.5-3.1 mm), though Substitution of the reactivated catalyst as described herein
they may be as large as 4th inch (6.35 mm). In a particular above; or: (4) a hybrid System with Semiregenerative and
regenerator, however, it is desirable to use catalyst particles continuous-regeneration provisions in the same Zone. The
which fall in a relatively narrow Size range. A preferred preferred embodiment of the present invention is a hybrid
catalyst particle diameter is /16th inch (3.1 mm). 25 System of a fixed-bed reactor in a Semiregenerative Zeolitic
An essential component of the first reforming catalyst is reforming Zone and a moving-bed reactor with continuous
one or more platinum-group metals, with a platinum com catalyst regeneration in the continuous-reforming Zone.
ponent being preferred. The platinum may exist within the The first reforming catalyst preferably represents about
catalyst as a compound Such as the oxide, Sulfide, halide, or 20% to 99% by volume of the total catalyst in the present
Oxyhalide, in chemical combination with one or more other reforming process. The relative Volumes of first and Zeolitic
ingredients of the catalytic composite, or as an elemental reforming catalyst depend on product objectives as well as
metal. Best results are obtained when substantially all of the whether the proceSS incorporates previously utilized equip
platinum exists in the catalytic composite in a reduced State. ment. If the product objective of an all-new process unit is
The platinum component generally comprises from about 35
maximum practical production of benzene and toluene from
0.01 to 2 mass % of the catalytic composite, preferably 0.05 a relatively light hydrocarbon feedstock, the Zeolitic reform
to 1 mass %, calculated on an elemental basis. ing catalyst advantageously comprises a Substantial
It is within the scope of the present invention that the first proportion, preferably about 10-60%, of the total catalyst. If
reforming catalyst contains a metal promoter to modify the a new Zeolitic-reforming Zone is added to an existing
effect of the preferred platinum component. Such metal 40
continuous-reforming Zone, on the other hand, the Zeolitic
modifiers may include Group IVA (14) metals, other Group reforming catalyst optimally comprises a relatively Small
VIII (8-10) metals, rhenium, indium, gallium, zinc, proportion of the total catalyst in order to minimize the
uranium, dySprosium, thallium and mixtures thereof. Excel impact of the new Section on the existing continuous
lent results are obtained when the first reforming catalyst reforming operation. In the latter case, preferably about 55%
contains a tin component. Catalytically effective amounts of 45
to 95% of the total catalyst volume of the process is
Such metal modifiers may be incorporated into the catalyst represented by the first reforming catalyst.
by any means known in the art. The addition of a Zeolitic-reforming Zone to an existing
The first reforming catalyst may contain a halogen com continuous-reforming Zone, i.e., an installation in which the
ponent. The halogen component may be either fluorine, major equipment for a moving-bed reforming unit with
chlorine, bromine or iodine or mixtures thereof. Chlorine is 50 continuous catalyst regeneration is in place, is a particularly
the preferred halogen component. The halogen component is advantageous embodiment of the present invention. A
generally present in a combined State with the inorganic continuous-regeneration reforming unit is relatively capital
oxide Support. The halogen component is preferably well intensive, generally being oriented to high-Severity reform
dispersed throughout the catalyst and may comprise from ing and including the additional equipment for continuous
more than 0.2 to about 15 wt.%. calculated on an elemental 55
catalyst regeneration. By adding on a Zeolitic-reforming
basis, of the final catalyst. Zone which is particularly effective in converting light
An optional ingredient of the first reforming catalyst is a paraffins from an first effluent produced by continuous
Zeolite, or crystalline aluminosilicate. Preferably, however, reforming, Some options would be open for improvement of
this catalyst contains Substantially no Zeolite component. the overall catalytic-reforming operation:
The first reforming catalyst may contain a non-Zeolitic 60 Increase Severity, in terms of Overall aromatics yields or
molecular sieve, as disclosed in U.S. Pat. No. 4,741,820 product octane number.
which is incorporated herein in by reference thereto. Increase throughput of the continuous-reforming Zone by
The first reforming catalyst generally will be dried at a at least about 5%, preferably at least about 10%,
temperature of from about 100° to 320° C. for about 0.5 to optionally at least 20%, and in some embodiments 30%
24 hours, followed by oxidation at a temperature of about 65 or more through reduced continuous-reforming Sever
300 to 550° C. in an air atmosphere for 0.5 to 10 hours. ity. Such reduced severity would be effected by one or
Preferably the oxidized catalyst is subjected to a substan more of operating at higher Space Velocity, lower
 5,935,415
10
hydrogen-to-hydrocarbon ratio and lower catalyst cir aromatics and concentration of nonaromatics. Usually the
culation in the continuous-reforming Zone. The maximum temperature in the Zeolitic-reforming Zone is
required product quality then would be effected by lower than that in the Zeolitic-reforming Zone, but the
processing the first effluent from the continuous temperature in the Zeolitic-reforming Zone may be higher
reforming Zone in the Zeolitic-reforming Zone. depending on catalyst condition and product objectives.
Increase Selectivity, reducing Severity of the continuous The Zeolitic-reforming Zone may comprises a single reac
reforming operation and Selectively converting residual tor containing the Zeolitic reforming catalyst or,
paraffins in the first effluent to aromatics. alternatively, two or more parallel reactors with Valving as
The first effluent from the continuous-reforming Zone known in the art to permit alternative cyclic regeneration.
passes to a Zeolitic-reforming Zone for completion of the The choice between a Single reactor and parallel cyclic
reforming reactions. Preferably free hydrogen accompany reactorS depends inter alia on the reactor Volume and the
ing the first effluent is not separated prior to the processing need to maintain a high degree of yield consistency without
of the first effluent in the Zeolitic-reforming Zone, i.e., the interruption; preferably, in any case, the reactors of the
continuous- and Zeolitic-reforming Zones are within the Zeolitic reforming Zone are valved for removal from the
Same hydrogen circuit. It is within the Scope of the invention 15 process combination So that the Zeolitic reforming catalyst
that a Supplementary naphtha feed is added to the first may be regenerated or replaced while the continuous
effluent as feed to the Zeolitic-reforming Zone to obtain a reforming Zone remains in operation.
Supplementary reformate product. The Supplementary naph In an alternative embodiment, it is within the ambit of the
tha feed has characteristics within the Scope of those invention that the Zeolitic-reforming Zone comprises two or
described for the hydrocarbon feedstock, but optimally is more reactors with interheating between reactors to raise the
lower-boiling and thus more favorable for production of temperature and maintain dehydrocyclization conditions.
lighter aromatics than the feed to the continuous-reforming This may be advantageous Since a major reaction occurring
Zone. The first effluent, and optionally the Supplementary in the Zeolitic-reforming Zone is the dehydrocyclization of
naphtha feed, contact a Zeolitic reforming catalyst at Second paraffins to aromatics along with the usual dehydrogenation
reforming conditions in the Zeolitic-reforming Zone. 25 of naphthenes, and the resulting endothermic heat of reac
The hydrocarbon feedstock contacts the Zeolitic reform tion may cool the reactants below the temperature at which
ing catalyst in the Zeolitic-reforming Zone to obtain an reforming takes place before Sufficient dehydrocyclization
aromatics-rich product, with a principal reaction being dehy has occurred.
drocyclization of paraffinic hydrocarbons remaining in the In another alternative embodiment, reforming tempera
first effluent. Second reforming conditions used in the ture may be maintained within the Zeolitic-reforming Zone
Zeolitic-reforming Zone of the present invention include a by inclusion of heat-exchange internals in a reactor of the
pressure of from about 100 kPa to 6 MPa (absolute), with the Zone. U.S. Pat. No. 4,810,472, for example, teaches a
preferred range being from 100 kPa to 1 MPa (absolute) and bayonet-tube arrangement for externally heating a reformer
a pressure of about 450 kPa or less at the exit of the last feed that passes through catalyst on the inside of the bayonet
reactor being especially preferred. Free hydrogen is Supplied 35 tube. U.S. Pat. No. 4,743,432 discloses a reactor having
to the Zeolitic-reforming Zone in an amount Sufficient to catalyst for the production of methanol disposed in beds
correspond to a ratio of from about 0.1 to 10 moles of with cooling tubes passing through the beds for removal of
hydrogen per mole of hydrocarbon feedstock, with the ratio heat. U.S. Pat. No. 4,820,495 depicts an ammonia- or
preferably being no more than about 6 and more preferably ether-Synthesis reactor having elongate compartments alter
no more than about 5. By “free hydrogen' is meant molecu 40 natively containing catalyst with reactants and a heat carrier
lar H, not combined in hydrocarbons or other compounds. fluid. Preferably a heat-exchange reactor is a radial-flow
The Volume of the contained Zeolitic reforming catalyst arrangement with flow channels in the form of Sectors which
corresponds to a liquid hourly Space Velocity of from about are contained in an annular volume of the reactor; a heat
1 to 40 hr, value of preferably at least about 7 hr' and eXchange medium and reactants contacting catalyst flow
optionally about 10 hr' or more. 45 radially through alternate channels, optimally in a counter
The operating temperature, defined as the maximum current arrangement. An arrangement of WebS Supports
temperature of the combined hydrocarbon feedstock, free thin-wall heat-exchange plates and provides flow
hydrogen, and any components accompanying the free distribution and -collection chambers on the inner and outer
hydrogen, generally is in the range of 260 to 560 C. This periphery of the channels.
temperature is Selected to achieve optimum overall results 50 The Zeolitic reforming catalyst contains a non-acidic
from the combination of the continuous- and Zeolitic Zeolite, an alkali-metal component and a platinum-group
reforming Zones with respect to yields of aromatics in the metal component. It is essential that the Zeolite, which
product, when chemical aromatics production is the preferably is LTL or L-Zeolite, be non-acidic Since acidity in
objective, or properties Such as octane number when gaso the Zeolite lowers the selectivity to aromatics of the finished
line is the objective. Hydrocarbon types in the feed stock 55 catalyst. In order to be “non-acidic,” the Zeolite has sub
also influence temperature Selection, as the Zeolitic reform Stantially all of its cationic exchange Sites occupied by
ing catalyst is particularly effective for dehydrocyclization nonhydrogen Species. Preferably the cations occupying the
of light paraffins. Naphthenes generally are dehydrogenated eXchangeable cation Sites will comprise one or more of the
to a large extent in the prior continuous-reforming reactor alkali metals, although other cationic Species may be
with a concomitant decline in temperature acroSS the catalyst 60 present. An especially preferred nonacidic L-Zeolite is
bed due to the endothermic heat of reaction. Initial reaction potassium-form L-Zeolite.
temperature generally is slowly increased during each period Generally the L-Zeolite is composited with a binder in
of operation to compensate for the inevitable catalyst deac order to provide a convenient form for use in the catalyst of
tivation. The temperature to the reactors of the continuous the present invention. The art teaches that any refractory
and Zeolitic-reforming Zones optimally are Staggered, i.e., 65 inorganic oxide binder is Suitable. One or more of Silica,
differ between reactors, in order to achieve product objec alumina or magnesia are preferred binder materials of the
tives with respect to such variables as ratios of the different present invention. Amorphous Silica is especially preferred,
 5,935,415
11 12
and excellent results are obtained when using a Synthetic Zeolitic-reforming Zone usually is passed through a cooling
white Silica powder precipitated as ultra-fine Spherical par Zone to a separation Zone. In the Separation Zone, typically
ticles from a water Solution. The silicabinder preferably is maintained at about 0 to 65 C., a hydrogen-rich gas is
nonacidic, contains less than 0.3 mass % Sulfate Salts, and Separated from a liquid phase. Most of the resultant
has a BET surface area of from about 120 to 160 m /g. hydrogen-rich Stream optimally is recycled through Suitable
The L-Zeolite and binder may be composited to form the compressing means back to the Zeolitic-reforming Zone,
desired catalyst shape by any method known in the art. For with a portion of the hydrogen being available as a net
example, potassium-form L-Zeolite and amorphous Silica product for use in other Sections of a petroleum refinery or
may be commingled as a uniform powder blend prior to chemical plant. The liquid phase from the Separation Zone is
introduction of a peptizing agent. An acqueous Solution normally withdrawn and processed in a fractionating System
comprising Sodium hydroxide is added to form an extrud in order to adjust the concentration of light hydrocarbons
able dough. The dough preferably will have a moisture and to obtain the aromatics-rich product.
content of from 30 to 50 mass % in order to form extrudates It is within the scope of the invention that the order of the
having acceptable integrity to withstand direct calcination. continuous-reforming Zone and the Zeolitic-reforming Zone
The resulting dough is extruded through a Suitably shaped 15 is reversed, i.e., an alternative embodiment is reforming of
and sized die to form extrudate particles, which are dried and a hydrocarbon feedstock with a Zeolitic catalyst to obtain an
calcined by known methods. Alternatively, Spherical par aromatized effluent which is processed in a moving-bed
ticles may be formed by methods described hereinabove for reforming unit with continuous catalyst regeneration to
the Zeolitic reforming catalyst. obtain an aromatics-rich product. Operating conditions and
An alkali-metal component is an essential constituent of catalysts for the two Zones are within the parameters
the Zeolitic reforming catalyst. One or more of the alkali described above. This embodiment may be termed pre
metals, including lithium, Sodium, potassium, rubidium, aromatization of a continuous-reforming feedstock, in which
cesium and mixtures thereof, may be used, with potassium the Zeolitic-reforming Zone effects dehydrocyclization of
being preferred. The alkali metal optimally will occupy paraffins prior to high-Severity reforming with continuous
essentially all of the cationic exchangeable sites of the 25 catalyst regeneration.
non-acidic L-Zeolite. Surface-deposited alkali metal also
may be present as described in U.S. Pat. No. 4,619,906, EXAMPLES
incorporated herein in by reference thereto. The following examples are presented to demonstrate the
A platinum-group metal component is another essential present invention and to illustrate certain Specific embodi
feature of the Zeolitic reforming catalyst, with a platinum ments thereof. These examples should not be construed to
component being preferred. The platinum may exist within
the catalyst as a compound Such as the oxide, Sulfide, halide, limit the Scope of the invention as Set forth in the claims.
or oxyhalide, in chemical combination with one or more There are many possible other variations, as those of ordi
other ingredients of the catalytic composite, or as an elemen nary skill in the art will recognize, which are within the spirit
of the invention.
tal metal. Best results are obtained when substantially all of 35
Three parameters are especially useful in evaluating
the platinum exists in the catalytic composite in a reduced
State. The platinum component generally comprises from reforming process and catalyst performance, particularly in
about 0.05 to 5 mass % of the catalytic composite, preferably evaluating catalysts for dehydrocyclization of paraffins.
0.05 to 2 mass %, calculated on an elemental basis. It is “Activity” is a measure of the catalyst’s ability to convert
within the Scope of the present invention that the catalyst 40 reactants at a specified Set of reaction conditions. "Selectiv
may contain other metal components known to modify the ity' is an indication of the catalyst's ability to produce a high
effect of the preferred platinum component. Such metal yield of the desired product. “Stability” is a measure of the
modifiers may include Group IVAC14) metals, other Group catalyst’s ability to maintain its activity and Selectivity over
time.
VIII(8-10) metals, rhenium, indium, gallium, zinc, uranium,
dySprosium, thallium and mixtures thereof. Catalytically 45 The examples present comparative results of pilot-plant
effective amounts of Such metal modifiers may be incorpo tests when processing a naphtha feedstock comprising prin
rated into the catalyst by any means known in the art. cipally C-C hydrocarbons. The naphtha feedstock had the
The final Zeolitic reforming catalyst generally will be following characteristics:
dried at a temperature of from about 100 to 320° C. for
about 0.5 to 24 hours, followed by oxidation at a temperature 50
Sp. gr. O.7283
of about 300° to 550° C. (preferably about 350° C) in an air ASTM D-86, C.:
atmosphere for 0.5 to 10 hours. Preferably the oxidized
catalyst is Subjected to a Substantially water-free reduction IBP 75
step at a temperature of about 300 to 550° C. (preferably 50%
EP
1OO
137
about 350° C.) for 0.5 to 10 hours or more. The duration of 55
Volume %
the reduction Step should be only as long as necessary to
reduce the platinum, in order to avoid pre-deactivation of the Paraffins 62.O
catalyst, and may be performed in-situ as part of the plant Naphthenes 28.5
Aromatics 9.5
Startup if a dry atmosphere is maintained. Further details of
the preparation and activation of embodiments of the Zeolitic 60
reforming catalyst are disclosed, e.g., in U.S. Pat. NoS. The comparative tests were effected over a range of con
4,619.906 (Lambert et al) and 4,822,762 (Ellig et al.), which versions of non-aromatics in the feedstock at corresponding
are incorporated into this Specification by reference thereto. conditions, comparing results from the multi-Zone process
The Zeolitic-reforming Zone produces an aromatics-rich combination of the invention with those from known,
product contained in a reformed effluent containing hydro 65 closely related reforming processes. Results are evaluated
gen and light hydrocarbons. Using techniques and equip on the basis of the yields of “BTX aromatics,” or benzene/
ment known in the art, the reformed effluent from the toluene/Xylene/ethylbenzene, representing the basic aro
 5,935,415
13 14
matic intermediates, and "Cs aromatics,” or Xylenes-- of the continuous-reforming Zone by shifting the final por
ethylbenzene, generally considered the target aromatic tion of the reaction to a Zeolitic-reforming Zone. This
intermediate on which modern aromatics complexes are advantage would be particularly significant in the situation
sized. of an existing continuous-reforming Zone with continuous
catalyst regeneration which cannot meet increasing needs
Example I for gasoline or aromatics. Through the present invention,
Reforming pilot-plant tests were performed based on the feedstock throughput is increased in this Zone along with a
known use of a Catalyst A, a continuously regenerable reduction in conversion without increasing catalyst circula
catalyst comprising 0.29 mass-% platinum and 0.30 mass-% tion rate and regeneration rate. Overall conversion in the
tin on chlorided alumina, to process the C-C feedstock combination is maintained by adding Substantially only a
described hereinabove. Operating pressure was about 450 reactor in a Zeolitic-reforming Zone contained in the same
kPa, liquid hourly space velocity was about 2.5 hr' and hydrogen circuit while achieving higher throughput.
molecular hydrogen was Supplied at a molar ratio to the This embodiment can be illustrated by an example
feedstock of about 6. Temperature was varied to obtain derived from the pilot-plant tests described hereinabove,
conversion of nonaromatic hydrocarbons in the range of 45
15 comparing an “original' case with only a continuous
to 77 mass %. BTX aromatics yields over the range of reforming Zone and a case of the invention in which a
conversion for this control example are plotted in FIG. 1. Zeolitic-reforming Zone is added in order to increase the
throughput of a process unit from an original value of
Example II 1,000,000 metric tons per year:
Reforming pilot-plant tests were performed based on the
multi-Zone process combination of the invention processing Original Invention
the C-C feedstock described hereinabove. Catalyst A was Throughput, 10 tons/year 1,000 1,300
as described in Example I, and was loaded in front of a Conversion of nonaromatics, mass-% 74 65
Catalyst B comprising 0.82 mass-% platinum on Silica 25 Catalyst circulation base 0.9x base
bound L-Zeolite. The volumetric ratio of Catalyst A to Hydrogen/feedstock, mole 6.O 4.5
Catalyst B was 75/25. Liquid hourly space velocity, hr'* 2.5 3.3
Yields, 103 tons/year:
The naphtha was charged to the reactor in a downflow
operation, thus contacting Catalysts A and B Successively. Cs+ product 894 1,185
Benzene 95 169
Operating pressure was about 450 kPa, overall liquid hourly Toluene 250 403
Space Velocity with respect to the combination of catalysts Cs aromatics 250 286
was about 2.5 hr', and hydrogen was Supplied at a molar Total BTX aromatics 595 858
ratio to the feedstock of about 4.5. Temperature was varied *in continuous-reforming Zone
to obtain about 50 to 87 mass % conversion of nonaromatic
hydrocarbons. 35
Space Velocity in the Zeolitic-reforming Zone is Set at 10
The results are plotted in FIG. 1 in comparison to the hr'. Catalyst volume and gas circulation usually are the
results of using Catalyst A only according to control limiting parameters in the throughput of a hydroprocessing
Example I. The catalyst combination showed a significant unit; liquid throughput often can be increased by 20-30% or
aromatics-yield increase over results based on control Cata 40
more with little or no hydraulic debottlenecking. Thus
lyst A. addition of a Zeolitic-reforming Zone comprising a reactor
containing a non-acidic Zeolite catalyst with possible minor
Example III modifications to other equipment results in an increase in
The yield structures of the control Catalyst A and the BTX aromatics production of about 44% according to the
combination Catalyst A/B of the invention were compared at 45
above example illustrating the present invention.
an equivalent conversion of 74% of the nonaromatics in the Example V
feedstock (respectively about 99.5 and 98.5 Research
Octane of the Cs+ product), Selected from the range of A Second Set of control reforming pilot-plant tests were
conversions in Examples I and II and expressed as mass-% performed based on the known use of the aforementioned
yield relative to the feedstock: 50 Catalysts A and B to process the C-C feedstock described
hereinabove. Operating pressure was about 450 kPa and
hydrogen was Supplied at a molar ratio to the feedstock of
Catalyst A Catalysts A/B about 6. Temperature was varied to obtain conversion of
Benzene 9.5 13.0 nonaromatic hydrocarbons in the range of 64 to 77 mass %
Toluene 25.0 31.0 55 for Catalyst A and 64 to 78 mass-% for Catalyst B. The
Cs aromatics 25.0 22.0 results are plotted in FIG. 2.
Total BTX aromatics 59.5 66.O
Hydrogen 3.6 4.0 Example VI
Cs+ product 89.4 91.2
An example of the reverse order of the preferred embodi
60 ment of the invention, which also is within the ambit of the
The catalyst combination of the invention demonstrated over invention, was tested in a pilot-plant operation. The naphtha
10% higher aromatics yields relative to the control, as well was charged to the reactor in a downflow operation, con
as higher hydrogen and higher Cs+ yields. tacting Catalysts B and A Successively. Operating preSSure
Example IV was about 450 kPa and hydrogen was supplied to the reactor
65 to provide a molar ratio to the feedstock of about 6.
Another advantage of the process combination of the Temperature was varied to obtain conversion of nonaromatic
invention may be realized through more effective utilization hydrocarbons in the range of 72 to 77 mass %.
 5,935,415
15 16
The results are plotted in FIG. 2 in comparison to the and a platinum-group metal component at Second
control results as described in Example V. The catalyst reforming conditions comprising a pressure of from
combination showed a significant aromatics-yield increase about 100 kPa to 6 MPa, a liquid hourly space velocity
relative to Catalyst A, comparable to Catalyst B. of from about 1 to 40 hr' and a temperature of from
about 260 to 560 C. to obtain an aromatized effluent
Example VII as feed to the continuous-reforming Zone.
The operating temperature of the Example VI proceSS 2. The process of claim 1 wherein the preSSure in each of
combination of the invention was Staggered to optimize the the continuous-reforming Zone and Zeolitic reforming Zone
environment of each catalyst. The temperature to the Zone is between about 100 kPa and 1 MPa.
containing Catalyst B was raised to 515 C. while the 3. The process of claim 1 wherein the pressure in each of
temperature to Catalyst A was maintained at 493 C. Results the continuous-reforming Zone and Zeolitic reforming Zone
were assessed on the basis of the Research octane number is about 450 kPa or less.
(RON) of the product from each of the staggered 4. The process of claim 1 wherein the hydrogen-to
temperature operation and the constant-temperature opera hydrocarbon mole ratio in the continuous-reforming Zone to
tion of Example VI: 15 obtain the aromatics-rich product is no more than about 5.
Staggered temperature 99.8 RON 5. The process of claim 1 wherein the liquid hourly space
Constant temperature 97.4 RON Velocity of the Zeolitic reforming Zone is at least about 7
hr.
Example VIII 6. The process of claim 1 wherein the liquid hourly Space
Velocity of the Zeolitic reforming Zone is at least about 10
Results from the three pilot-plant runs presented in hr.
Examples V and VI were compared with respect to yields of 7. The process of claim 1 wherein the platinum-group
the desired BTX and C-aromatics products: metal component of the reconditioned reforming catalyst
comprises a platinum component.
Catalysts B/A Catalyst B Catalyst A 25 8. The process of claim 1 wherein the refractory inorganic
(Invention) (Known) (Known) oxide of the reconditioned reforming catalyst comprises
alumina.
BTX aromatics, mass % 67 68 61 9. The process of claim 1 wherein the reconditioned
Cs aromatics 76 23 17.5 25 reforming catalyst further comprises a metal promoter con
sisting of one or more of the Group IVA (14) metals,
The reverse proceSS combination of the invention yields rhenium, indium or mixtures thereof.
Substantially more Cs aromatics than known Catalyst A with 10. The process of claim 1 wherein the nonacidic zeolite
only a small sacrifice in overall BTX aromatics and Sub comprises potassium-form L-Zeolite.
stantially more BTX than Catalyst B with a relatively small 11. The process of claim 1 wherein the alkali-metal
reduction in Cs aromatics. 35 component comprises a potassium component.
We claim: 12. The process of claim 1 wherein the platinum-group
1. In a process for catalytically reforming a hydrocarbon metal component of the Zeolitic reforming catalyst com
feedstock distilling substantially within the range of 40 and prises a platinum component.
210 C. comprising contacting the hydrocarbon feedstock in 13. In a process for catalytically reforming a hydrocarbon
the presence of free hydrogen in a continuous-reforming 40 feedstock distilling substantially within the range of 40 and
Zone with reconditioned bifunctional reforming catalyst 210 C. comprising contacting the hydrocarbon feedstock in
particles comprising a platinum-group metal component, a the presence of free hydrogen in a continuous-reforming
halogen component and a refractory inorganic oxide at first Zone with reconditioned bifunctional reforming catalyst
reforming conditions comprising a preSSure of from about particles comprising a platinum-group metal component, a
100 kPa to 1 MPa, liquid hourly space velocity of from about 45 halogen component and a refractory inorganic oxide at first
0.2 to 10 hr', mole ratio of hydrogen to Cs+ hydrocarbons reforming conditions comprising a preSSure of from about
of about 0.1 to 10, and temperature of from about 400 to 100 kPa to 1 MPa, liquid hourly space velocity of from about
560° C. to produce an original first effluent containing BTX 0.2 to 10 hr', mole ratio of hydrogen to Cs+ hydrocarbons
aromatics and a base amount of deactivated catalyst of about 0.1 to 10, and temperature of from about 400 to
particles, removing the deactivated catalyst particles at least 50 560 C. to produce an original first effluent containing BTX
Semicontinuously from the continuous-reforming Zone and aromatics and a base amount of deactivated catalyst
contacting at least a portion of the particles Sequentially in particles, removing the deactivated catalyst particles at least
a continuous-regeneration Zone with an oxygen-containing Semicontinuously from the continuous-reforming Zone and
gas and in a reduction Zone with a hydrogen-containing gas contacting at least a portion of the particles Sequentially in
to obtain reconditioned catalyst particles, 55 a continuous-regeneration Zone with an oxygen-containing
the improvement comprising increasing the throughput of gas and in a reduction Zone with a hydrogen-containing gas
the continuous-reforming Zone by at least about 5 to obtain reconditioned catalyst particles,
Volume-% with a concomitant increase in Space Veloc the improvement comprising increasing the throughput of
ity and decrease in hydrogen-to-hydrocarbon mole the continuous-reforming Zone by at least about 5
ratio in the range of about 0.1 to 6 with no increase in 60 Volume-% with a concomitant increase in Space Veloc
the amount of deactivated catalyst particles over the ity and decrease in hydrogen-to-hydrocarbon mole
base amount to obtain an aromatics-rich product con ratio in the range of about 0.1 to 6 with no increase in
taining at least about 10% more BTX aromatics than the amount of deactivated catalyst particles over the
the original first effluent by contacting the naphtha base amount to obtain an aromatics-rich product con
feedstock prior to the first reforming Zone in a Zeolitic 65 taining at least about 10% more BTX aromatics than
reforming Zone with a Zeolitic reforming catalyst com the original first effluent by contacting the hydrocarbon
prising a non-acidic Zeolite, an alkali metal component feedstock prior to the first reforming Zone in a Zeolitic
 5,935,415
17 18
reforming Zone with a Zeolitic reforming catalyst com particles, removing the deactivated catalyst particles at least
prising a non-acidic Zeolite, an alkali metal component Semicontinuously from the continuous-reforming Zone and
and a platinum-group metal component at Second contacting at least a portion of the particles Sequentially in
reforming conditions comprising a pressure of from a continuous-regeneration Zone with an oxygen-containing
about 100 kPa to 6 MPa, a liquid hourly space velocity gas, in a redispersion Zone with a chlorine-containing gas
of from about 7 to 40 hr' and a temperature of from and in a reduction Zone with a hydrogen-containing gas to
about 260 to 560 C. to obtain an aromatized effluent obtain reconditioned catalyst particles,
as feed to the continuous-reforming Zone. the improvement comprising increasing the throughput of
14. The process of claim 13 wherein the regenerated the continuous-reforming Zone by at least about 5
catalyst particles are Subjected to a redispersion Step using a Volume-% with a concomitant increase in Space Veloc
chlorine-containing gas at about 425 to 600 C. to redis ity and decrease in hydrogen-to-hydrocarbon mole
perse the platinum-group metal on the catalyst particles and ratio in the range of about 0.1 to 6 with no increase in
obtain redispersed catalyst particles which are contacted in the amount of deactivated catalyst particles over the
the reduction Zone. base amount to obtain an aromatics-rich product con
15. In a process for catalytically reforming a hydrocarbon 15 taining at least about 10% more BTX aromatics than
feedstock distilling substantially within the range of 40 and the original first effluent by contacting the hydrocarbon
210 C. comprising contacting the hydrocarbon feedstock in feedstock prior to the first reforming Zone in a Zeolitic
the presence of free hydrogen in a continuous-reforming reforming Zone with a Zeolitic reforming catalyst com
Zone with reconditioned bifunctional reforming catalyst prising a non-acidic Zeolite, an alkali metal component
particles comprising a platinum-group metal component, a and a platinum-group metal component at Second
halogen component and a refractory inorganic oxide at first reforming conditions comprising a pressure of from
reforming conditions comprising a preSSure of from about about 100 to 450 kPa, a liquid hourly space velocity of
100 to 450 kPa, liquid hourly space velocity of from about from about 7 to 40 hr' and a temperature of from about
0.2 to 10 hr', mole ratio of hydrogen to Cs+ hydrocarbons 260 to 560° C. to obtain an aromatized effluent as feed
of about 0.1 to 10, and temperature of from about 400 to 25 to the continuous-reforming Zone.
560° C. to produce an original first effluent containing BTX
aromatics and a base amount of deactivated catalyst k k k k k