FIELD OF THE INVENTION
[0001] The present invention relates to a two stage process for catalytically reforming
a gasoline boiling range hydrocarbonaceous feedstock. The reforming is conducted in
two stages wherein the first stage is operated in a fixed bed mode, and the second
stage is operated in a moving-bed continual catalyst regeneration mode. A gaseous
stream comprised of hydrogen and predominantly C
4- hydrocarbon gases are separated between stages and at least a portion of it is recycled.
BACKGROUND OF THE INVENTION
[0002] Catalytic reforming is a well established refinery process for improving the octane
quality of naphthas or straight run gasolines. Reforming can be defined as the total
effect of the molecular changes, or hydrocarbon reactions, produced by dehydrogenation
of cyclohexanes, dehydroisomerization of alkylcyclopentanes, and dehydrocyclization
of paraffins and olefins to yield aromatics; isomerization of substituted aromatics;
and hydrocracking of paraffins which produces gas, and inevitably coke, the latter
being deposited on the catalyst. In catalytic reforming, a multifunctional catalyst
is usually employed which contains a metal hydrogenation-dehydrogenation (hydrogen
transfer) component, or components, usually platinum, substantially atomically dispersed
on the surface of a porous, inorganic oxide support, such as alumina. The support,
which usually contains a halide, particularly chloride, provides the acid functionality
needed for isomerization, cyclization, and hydrocracking reactions.
[0003] Reforming reactions are both endothermic and exothermic, the former being predominant,
particularly in the early stages of reforming with the latter being predominant in
the latter stages. In view thereof, it has become the practice to employ a reforming
unit comprised of a plurality of serially connected reactors with provision for heating
the reaction stream as it passes from one reactor to another. There are three major
types of reforming: semi-regenerative, cyclic, and continuous. Fixed-bed reactors
are usually employed in semi-regenerative and cyclic reforming, and moving-bed reactors
in continuous reforming. In semi-regenerative reforming, the entire reforming process
unit is operated by gradually and progressively increasing the temperature to compensate
for deactivation of the catalyst caused by coke deposition, until finally the entire
unit is shut-down for regeneration and reactivation of the catalyst. In cyclic reforming,
the reactors are individually isolated, or in effect swung out of line, by various
piping arrangements. The catalyst is regenerated by removing coke deposits, and then
reactivated while the other reactors of the series remain on stream. The "swing reactor"
temporarily replaces a reactor which is removed from the series for regeneration and
reactivation of the catalyst, which is then put back in the series. In continuous
reforming, the reactors are moving-bed reactors, as opposed to fixed-bed reactors,
with continuous addition and withdrawal of catalyst. The catalyst descends the reactor
in an annular bed and is passed to a regeneration zone where it is regenerated, the
sent back to the reforming zone. This cycle is continuously repeated.
[0004] With the gradual phasing out of lead from the gasoline pool and with the introduction
of premium grade lead-free gasoline in Europe and the U.S., petroleum refiners must
re-evaluate how certain refinery units are run to meet this changing demand. Because
catalytic reforming units produce product streams which represent the heart of the
gasoline pool, demands are being put on these units for generating streams with ever
higher octane ratings.
[0005] U.S. Patent No. 3,992,465 teaches a two stage reforming process wherein the first
stage is comprised of at least one fixed-bed reforming zone and the second stage is
comprised of a moving-bed reforming zone. The teaching of U.S. Patent No. 3,992,465
is primarily to subject the reformate, after second stage reforming to a series of
fractionations and an extractive distillation of the C
6-C
7 cut to obtain an aromatic-rich stream.
[0006] While these process schemes have commercial promise, the partially reformed stream
must still undergo a separation between stages to remove the heavier components before
they can be passed to a low pressure stage. This is because reforming reactors operated
in semiregenerative and cyclic modes cannot operate with a full range first stage
product stream at low pressure and low hydrogen/oil ratio typified by such processes.
A full range product stream at such conditions would cause too much carbon, or coke,
to deposit on the catalyst, thus leading to rapid catalyst deactivation.
[0007] Therefore, there still remains a need in the art for improved reforming processes
which can overcome such disadvantages.
[0008] GB-A-1469681 discloses and claims a multiple-stage process for the catalytic reforming
of a hydrocarbon feed stream which comprises the steps of:
(a) reacting said feed stream in a plurality of catalytic first reaction zones containing
non-movable fixed beds of catalyst, said feed stream contacting the individual fixed
beds of catalyst in lateral, radial flow, and said fixed beds being arranged in series
flow with each other;
(b) introducing at least a portion of the resulting first zone effluent downwardly
into a second reaction zone containing a bed of catalyst movable downwardly therethrough
via gravity-flow, and further reacting said effluent in contact with said movable
catalyst;
(c) withdrawing, at least periodically, catalyst from said second reaction zone, while
simultaneously recovering converted hydrocarbon effluent therefrom; and,
(d) at least periodically adding fresh, or regenerated catalyst to said second reaction
zone.
[0009] US-A-4985132 discloses and claims a process for the catalytic reforming of hydrocarbons
comprising contacting the hydrocarbon feed in two sequential catalyst zones, wherein:
(a) an initial catalyst zone which is a fixed-bed system and contains an initial catalytic
composite comprising a platinum component, a germanium component, a refractory inorganic
oxide, and a halogen component; and
(b) a terminal catalyst zone which is a moving-bed system with associated continuous
catalyst regeneration and contains a terminal catalytic composite having the essential
absence of germanium and comprising a platinum component, a refractory inorganic oxide,
a halogen component, and catalytically effective amounts of a metal promoter selected
from one or more of the rhenium, tin, indium, rhodium, ruthenium, cobalt, nickel,
and iridium.
[0010] In accordance with the present invention, there is provided a process for catalytically
reforming a gasoline boiling range hydrocarbon reactant stream in the presence of
hydrogen in a reforming process unit comprised of a plurality of serially connected
reforming zones wherein each of the reforming zones contains a catalyst comprised
of one or more Group VIII noble metals on a refractory support. The catalyst may be
either monofunctional or bifunctional. The process comprises:
(a) reforming the reactant stream in a first reforming stage comprised of one or more
serially connected reforming zones containing a fixed-bed of catalyst comprised of
one or more Group VIII noble metals on a refractory support, which one or more reforming
zones are operated at reforming conditions which includes a gauge pressure of about
100 to 500 psi (6.896 to 34.48 bar) and a H2:C5+ mol ratio in the range of from 1 to 10, thereby producing a first effluent stream;
(b) passing said first effluent stream to a separation zone wherein a hydrogen-rich
predominantly C4- hydrocarbon gaseous stream and a predominantly C5+ effluent stream; are produced
(c) recycling a portion of the hydrogen-rich gaseous stream to said first reforming
stage;
(d) reforming the C5+ effluent stream with the remaining portion of the hydrogen-rich gaseous stream in
a second reforming stage operated at a pressure which is at least 50 psi (3.45 bar)
lower than that of the first reforming stage and a H2:oil mol ratio of from 0.5 to 5.0 , which second reforming stage is comprised of one
or more serially connected reforming zones which are operated in a moving-bed continual
catalyst regeneration mode wherein the catalyst descends through the reforming zone,
exits, and is passed to a regeneration zone where any accumulated carbon is burned-off,
and wherein the regenerated catalyst is recycled to the one or more moving-bed reforming
zones.
[0011] In preferred embodiments, the Group VIII noble metal for catalysts in all stages
is platinum and the catalyst of the first stage is comprised of platinum and tin on
substantially spherical alumina support particles.
[0012] In yet another preferred embodiment of the present invention, from about 50 to 85
vol.% of the hydrogen-rich gas separated between stages is recycled.
[0013] In still other embodiment of the present invention an aromatics-rich stream is separated
and collected between stages and the remaining aromatics-lean stage is sent to second
stage reforming.
BRIEF DESCRIPTION OF THE FIGURE
[0014] The sole figure hereof depicts a simplified flow diagram of a preferred reforming
process of the present invention. The reforming process unit is comprised of a first
stage which includes a lead reforming zone, which is represented by a lead fixed-bed
reactor, and a first downstream fixed-bed reforming zone, which is represented by
another fixed-bed reactor, which first stage is operated in semi-regenerative mode,
but which may also be designed to operate in a cyclic mode. There is also a second
stage which contains two serially connected moving-bed reforming zones in fluid communication
with a regeneration zone, which reforming zones are represented by annular radial
flow reactors wherein the catalyst continuously descends through the reactors and
is transported to the regeneration zone, then back to the reactors, etc.
DETAILED DESCRIPTION OF THE INVENTION
[0015] Feedstocks, also sometimes referred to herein as reactant streams, which are suitable
for reforming in accordance with the instant invention are any hydrocarbonaceous feedstocks
boiling in the gasoline range. Nonlimiting examples of such feedstocks include the
light hydrocarbon oils, boiling from about 70° F (21.1°C) to about 500° F (260°C),
preferably from about 180° F (82.2°C) to about 400° F (204.4°C), for example straight
run naphthas, synthetically produced naphthas such as coal and oil-shale derived naphthas,
thermally or catalytically cracked naphthas, hydrocracked naphthas, or blends or fractions
thereof.
[0016] Referring to the sole Figure hereof, a gasoline boiling range hydrocarbon reactant
stream, which is preferably first hydrotreated by any conventional hydrotreating method
to remove undesirable components such as sulfur and nitrogen, is passed to a first
reforming stage represented by heater or preheat furnaces, F
1 and F
2, and reactors R
1 and R
2. A reforming stage, as used herein, is any one or more of a particular type of reforming
zone, in this figure reactors, and its associated equipment (e.g., preheat furnaces
etc.). That is, each reforming stage will contain one or more of the same type of
reactor, for example, fixed-bed or moving-bed, but not both. The reactant stream is
fed into heater, or preheat furnace, F
1, via line 10 where it is heated to an effective reforming temperature. That is, to
a temperature high enough to initiate and maintain dehydrogenation reactions, but
not so high as to cause excessive hydrocracking. The heated reactant stream is then
fed, via line 12, into reforming zone R
1 which contains a catalyst suitable for reforming. Such a catalyst typically contains
at least one Group VIII noble metal, preferably platinum, with or without a promoter
metal, on a refractory support, preferably alumina. Reforming zone R
1, as well as all the other reforming zones in this first stage, are operated at reforming
conditions. Typical reforming operating conditions for the reactors of this first
fixed-bed stage include temperatures from about 800° to about 1200° F (426.7 to 648.9°C);
gauge pressures from 100 psig (6.896 bar) to 500 psig (34.48 bar), preferably from
about 150 psig (10.34 bar) to about 300 psig (20.69 bar): a weight hourly space velocity
(WHSV) of about 0.5 to about 20, preferably from about 0.75 to about 5 and a hydrogen
to oil ratio of 1 to 10 moles of hydrogen per mole of C
5+ feed, preferably 1.5 to 5 moles of hydrogen per mole of C
5+ feed.
[0017] The effluent stream from reforming zone R
1 is fed to preheat furnace F
2 via line 14, then to reforming zone R
2 via line 16. Because reforming reactions are typically endothermic, the reactant
stream must be reheated to reforming temperatures between reforming zones. The effluent
stream from this first stage is sent to cooling zone K
1 via line 18 where it is cooled to condense a liquid phase to a temperature within
the operating range of the recycle gas separation zone, which is represented in the
Figure hereof by a separation drum S
1. The temperature will generally range from about 60° to about 300° F (15.6 to 148.9°C),
preferably from about 80 to 125°F (26.7 to 51.7°C).The cooled effluent stream is then
fed to separation zone S
1 via line 20 where a gaseous stream and a heavier liquid stream are produced. The
preferred separation would result in a hydrogen-rich predominantly C
4- gaseous stream and a predominantly C
5+ liquid stream. It Is understood that these streams are not pure streams. For example,
the separation zone will not provide complete separation between the C
4- components and the C
5+ liquids. Thus, the gaseous stream will contain minor amounts of C
5+ components and the liquid stream will contain minor amounts of C
4- components and hydrogen.
[0018] A portion of the gaseous stream, which can be characterized as being a hydrogen-rich
C
4- gaseous stream, is recycled, via line 22, to line 10 by first passing it through
compressor C
1 to increase its pressure to feedstock pressure. About 40 to 90 vol.%, preferably
about 50 to 85 vol.%, of the hydrogen-rich gaseous stream will be recycled. Of course,
during start-up, the unit is pressured-up with hydrogen from an independent source
until enough hydrogen can be generated in the first stage for recycle. It is preferred
that the first stage be operated in semi-regenerative mode, although a cyclic mode
can also be used.
[0019] The remaining hydrogen-rich predominantly C
4- gaseous stream from separation zone S
1 is passed to the second reforming stage via pressure control valve 26 where pressure
is reduced to the level required for second stage operation. The amount of pressure
reduction will depend on the operating pressure of the second stage separation zone
S
2 and the pressure drop in furnaces F
3 and F
4, reactors R
3 and R
4, and the connecting piping. The reduced pressure gas from line 25 is mixed with the
C
5+ liquid which passes from separation zone S
1 through a level control valve (not shown) and the mixture is then passed via line
24 to furnace F
3.
[0020] The heated stream from furnace F
3 is passed to reforming zone R
3 via line 28, which is operated in a moving-bed continual catalyst regeneration mode.
Reforming conditions for the moving-bed reforming zones will include temperatures
from about 800° to 1200° F (426.7 to 648.9°C), preferably from about 800° to 1000°
F (426.7 to 537.8°C); pressures gauge from about 30 to 300 (2.07 to 20.68 bar), preferably
from about 50 to 150 psig (3.5 to 10.3 bar); a weight hourly space velocity from about
0.5 to 20, preferably from about 0.75 to 6. Hydrogen-rich gas should be provided to
maintain the hydrogen to oil ratio between the range of about 0.5 to 5, preferably
from about 0.75 to 3. In the preferred embodiment, all of the hydrogen gas is supplied
by the hydrogen-rich predominantly C
4- gaseous stream which passes through pressure control valve 26. Instances may exist
in which the gas flowing from the first stage is insufficient to supply the needed
hydrogen to oil ratio. This could occur if the feedstock to the first stage was highly
paraffinic or had a boiling range which included predominantly hydrocarbons in the
6 to 8 carbon number range. In these instances, hydrogen would need to be supplied
from external sources such as a second reforming unit or a hydrogen plant. An additional,
but less preferred source of hydrogen would be from compressing and recycling stream
56. This option would require additional compressor or a larger capacity compressor
C
2.
[0021] Such reforming zones, or reactors, are well known in the art and are typical of those
taught in U.S. Patent Nos. US-A-3,652,231; 3,856,662; 4,167,473; and 3,992,465.
[0022] The general principle of operation of such reforming zones is that the catalyst is
contained in a annular bed formed by spaced cylindrical screens within the reactor.
The reactant stream is processed through the catalyst bed, typically in an out-to-in
radial flow, that is, it enters the reactor at the top and flows radially from the
reactor wall through the annular bed of catalyst 30 which is descending through the
reactor, and passes into the cylindrical space 32 created by said annular bed. It
exits the bottom of the reforming zone and is passed, via line 34, to furnace F
4, then to reforming zone R
4 via line 35. Again, as in reforming zone R
3, the reactant stream passes out-to-in radially through the catalyst bed and into
the cylindrical space 44 defined by said annular bed of catalyst. The effluent stream
from reforming zone R
4 is passed via line 46 to cooling zone K
2 where the temperature of the stream is dropped to about 60° to 200°F (15.6 to 93.3°C),
preferably from about 80° to 125°F (26.7 to 51.7°C). It is then passed into separation
zone S
2 via line 52 where it is separated into a light hydrogen-rich C
4- gaseous stream and a C
5+ liquid stream. The C
5+ stream is collected for blending in the gasoline pool via line 54, and the light
hydrogen-rich C
4- gaseous stream is sent through compressor C
2 via line 56 and used as a product gas.
[0023] Fresh and/or regenerated catalyst is charged to reforming zone R
3 by way of line 33 and distributed in the annular moving-bed 30 by means of catalyst
transfer conduits 36, the catalyst being processed downwardly as an annular dense-phase
moving bed. The reforming catalyst charged to reforming zones R
3 and R
4 is comprised of at least one Group VIII noble metal, preferably platinum; and one
or more promoter metals, preferably tin, on spherical particles of a refractory support,
preferably alumina. The spherical particles have an average diameter of about 1 to
3 mm, preferably about 1.5 to 2 mm, the bulk density of this solid being from about
0.5 to 0.9 and more particularly from about 0.5 to 0.8. The annular moving bed of
catalyst exits from the bottom section of reforming zone R
3 and is passed via line 38 to reforming zone R
4 where it is distributed into the annular moving catalyst bed 42 by transfer from
conduits 40.
[0024] The catalyst of reforming zone R
4 descends through the zone where it exits and is passed to catalyst regeneration zone
CR via line 48 and transfer conduit 50 where the catalyst is subjected to one or more
steps common to the practice of reforming catalyst regeneration. The catalyst regeneration
zone CR represents all of the steps required to remove at least a portion of the carbon
from the catalyst and return it to the state needed for the reforming reactions occurring
in reforming zone R
3. The specific steps included in CR will vary with the selected catalyst. The only
required step is one where accumulated carbon is burned-off at temperatures from about
600° to 1200°F (315.6 to 648.9°C) and in the presence of an oxygen-containing gas,
preferably air. Additional steps which may also be contained in the catalyst regeneration
equipment represented by CR include, but are not limited to, adding a halide to the
catalyst, purging carbon oxides, redispersing metals, and adding sulfur or other compounds
to lower the rate of cracking when the catalyst first enters the reforming zone.
[0025] The regenerated catalyst is then charged to reforming zone R
3 via line 33 and the cycle of continuous catalyst regeneration is continued until
the entire reforming unit (both stages) is shut down, such as for catalyst regeneration
of first stage (fixed-bed) reforming, which if operated in a semi-regenerative mode
would need to be regenerated from time to time by shutting off the feed and raising
the reactors to regeneration temperatures in the presence of an oxygen-containing
gas. It is to be understood that the catalyst in the moving-bed reforming and regeneration
zones may not be constantly moving, but may only move intermittently through the system.
This may be caused by the opening an closing of various valves in the system. Thus,
the word "continuous" is not to be taken literally and the word "continual" is sometimes
used interchangeably with "continuous".
[0026] The moving-bed zones of the second stage may be arranged in series, side-by-side,
each of then containing a reforming catalyst bed slowly flowing downwardly, as mentioned
above, either continuously or, more generally, periodically, said bed forming an uninterrupted
column of catalyst particles. The moving bed zones may also be vertically stacked
in a single reactor, one above the other, so as to ensure the downward flow of catalyst
by gravity from the upper zone to the next below. The reactor then consists of reaction
zones of relatively large sections through which the reactant stream, which is in
a gaseous state, flows from the periphery of the interior of the reactor (although
a reactor may be designed to have the reactant stream flow from the center to the
periphery) to the center (or from the center to the periphery) interconnected by catalyst
zones of relatively small sections, the reactant stream issuing from one catalyst
zone of large section divided into a first portion (preferably from 1 to 10%) passing
through a reaction zone of small section for feeding the subsequent reaction zone
of large section and a second portion (preferably from 99 to 90%) sent to a thermal
exchange zone and admixed again to the first portion of the reactant stream at the
inlet of the subsequent catalyst zone of large section.
[0027] When using one or more reaction zones with a moving bed of catalyst, said zones as
well as the regeneration zone, are generally at different levels. It is therefore
necessary to ensure several times the transportation of the catalyst from one relatively
low point to a relatively high point, for example from the bottom of a reaction zone
to the top of the regeneration zone, said transportation being achieved by any lifting
device simply called "lift' (not shown on the Figure hereof). The fluid of the lift
used for conveying the catalyst may be any convenient gas, for example nitrogen or
still for example hydrogen and more particularly purified hydrogen or recycle hydrogen.
[0028] Catalysts suitable for use in any of the reactors of any of the stages include both
monofunctional and bifunctional, monometallic and multimetallic noble metal containing
reforming catalysts. Preferred are the bifunctional reforming catalysts comprised
of a hydrogenation-dehydrogenation function and an acid function. The acid function,
which is important for isomerization reactions, is thought to be associated with a
material of the porous, adsorptive, refractory oxide type which serves as the support,
or carrier, for the metal component, usually a Group VIII noble metal, preferably
Pt, to which is generally attributed the hydrogenation-dehydrogenation function. The
preferred support for both stages of reforming is an alumina material, more preferably
gamma alumina. It is understood that the support material for the second stage reforming
must be in the form of particles which are substantially spherical in shape, as previously
described. One or more promoter metals selected from metals of Groups IIIA, IVA, IB,
VIB, and VIIB of the Periodic Table of the Elements may also be present. The promoter
metal, can be present in the form of an oxide, sulfide, or in the elemental state
in an amount from about 0.01 to about 5 wt.%, preferably from about 0.1 to about 3
wt.%, and more preferably from about 0.2 to about 3 wt.%, calculated on an elemental
basis, and based on total weight of the catalyst composition. It is also preferred
that the catalyst compositions have a relatively high surface area, for example, about
100 to 250 m
2/g. The Periodic Table of which all the Groups herein refer to can be found on the
last page of Advanced Inorganic Chemistry, 2nd Edition, 1966, Interscience publishers,
by Cotton and Wilkinson.
[0029] The acid function of the catalyst is typically provided by a halide component which
may be fluoride, chloride, iodide bromide, or mixtures thereof. Of these, fluoride,
and particularly chloride, are preferred. Generally, the amount of halide is such
that the final catalyst composition will contain from about 0.1 to about 3.5 wt.%,
preferably from about 0.5 to about 1.5 wt.% of halogen calculated on an elemental
basis.
[0030] Preferably, the Group III noble metal, the most preferred which is platinum, will
be present on the catalyst in an amount from about 0.01 to about 5 wt.%, calculated
on an elemental basis, of the final catalytic composition. More preferably, the catalyst
comprises from about 0.1 to about 2 wt.% platinum group component, especially about
0.1 to 2 wt.% platinum. Other preferred platinum group metals include palladium, iridium,
rhodium, osmium, ruthenium and mixtures thereof.
[0031] By practice of the present invention, reforming is conducted more efficiently and
results in increased hydrogen and C
5+ liquid yields. The first stage reactors are operated at conventional reforming temperatures
and pressures in semiregenerative or cyclic mode while the reactors of the second
stage are moving bed reactors operated substantially at lower pressures. Such (gauge)
pressures in the second stage may be from as low as about 30 psig to about 100 psig
(2.07 to 6.89 bar). More particularly, the downstream reactors can be operated in
once-through gas mode because there is an adequate amount of hydrogen generated, that
when combined with the hydrogen-rich gas stream from the first stage, is an adequate
amount of hydrogen to sustain the reforming reactions taking place.
[0032] The second stage reactors, when operated in a once-through hydrogen-rich gas mode,
permit a smaller product-gas compressor (C
2 in the Figure) to be substituted for a larger capacity recycle gas compressor. Pressure
drop in the second stage is also reduced by virtue of once-through gas operation.
Of course, the second stage reactors can be operated in a mode wherein the hydrogen-rich
gas is recycled.
[0033] It is also within the scope of this invention that an aromatics separation unit where
aromatic materials are separated in one or more steps to produce an aromatics-rich
stream, an aromatics-lean stream, and optionally a stream containing predominantly
C
5 and lighter hydrocarbons which comprise a portion of the aromatics-lean stream. This
optional stream might be required to effect an economical separation of the remaining
C
6+ product and can be removed as product or may be mixed back with the aromatics-rich
stream for processing in the second stage. The terms "aromatics-rich" and "aromatics-lean"
as used herein refer to the level of aromatics in the liquid fraction reaction stream
after aromatic separation relative to the level of aromatics prior to separation.
That is, after a reaction stream is subjected to an aromatics separation, two fractions
result. One fraction has a higher level of aromatics relative to the stream before
separation and is thus referred to as the aromatics-rich fraction. The other fraction
is, of course, the aromatics-lean fraction which can also be referred to as the paraffin-rich
fraction. Aromatics separation can be accomplished by any suitable method. Non-limiting
methods suitable for use herein for aromatics separation include: extraction, extractive
distillation, distillation, flashing, adsorption, and by permeation through a semipermeable
membrane, or by any other appropriate aromatics or paraffins removal process. Preferred
are extractive distillation, distillation, and flashing.
1. A process for catalytically reforming a gasoline boiling range hydrocarbon reactant
stream in the presence of hydrogen In a reforming process unit comprised of a plurality
of serially connected reforming zones wherein each of the reforming zones contains
a reforming catalyst comprised of at least one Group VIII noble metal on a refractory
support, which process comprises;
(a) reforming the reactant stream in a first reforming stage comprised of one or more
serially connected reforming zones containing a fixed-bed of catalyst comprised of
one or more Group VIII noble metals on a refractory support, which one or more reforming
zones are operated at reforming conditions which includes a (gauge) pressure of from
100 to 500 psig (6.896 to 34.48 bar), and a H2:C5+ mol ratio in the range of from 1 to 10, thereby producing a first effluent stream;
(b) passing said first effluent stream to a separation zone wherein a hydrogen-rich
predominantly C4- hydrocarbon gaseous stream and a predominantly C5+ effluent stream; are produced
(c) recycling a portion of the hydrogen-rich gaseous stream to said first reforming
stage;
(d) reforming the C5+ effluent stream, with the remaining portion of the hydrogen-rich gaseous stream,
in a second reforming stage operated at a pressure which is at least 50 psi (3.45
bar) lower than that of the first reforming stage and a H2:oil mol ratio of from 0.5 to 5.0, which second reforming stage is comprised of one
or more serially connected reforming zones which are operated in a moving-bed continual
catalyst regeneration mode, which catalyst is comprised of at one or more Group VIII
noble metals on substantially spherical refractory support particles, wherein the
catalyst continually descends through the reforming zone, exits, and Is passed to
a regeneration zone where it is regenerated by burning-off at least a portion of any
accumulated carbon, and wherein the regenerated catalyst is continually recycled back
to the one or more reforming zones.
2. The process of claim 1 wherein the catalyst in each of the reforming zones of the
first stage is comprised of from 0.01 to 5 wt.% platinum, and from 0.01 to 5 wt.%
of at least one metal selected from the group consisting of iridium, rhenium, and
tin.
3. The process of claim 1 or claim 2 wherein: (i) the first reforming stage contains
2 or 3 fixed-bed reforming zones, and (ii) the second reforming stage contains one
or two moving-bed reforming zones, with the proviso that when two moving-bed reforming
zones are employed, the catalyst descends through a first moving-bed reforming zone,
is passed to a second moving-bed reforming zone where it descends through said second
moving-bed reforming zone, then is passed to a regeneration zone where any accumulated
carbon is burned-off, after which the regenerated catalyst is recycled to said first
moving-bed reforming zone.
4. The process of any one of claims 1 to 3 wherein: (i) aromatics are separated from
at least a portion of the reaction stream of the first reforming stage thereby producing
an aromatics-rich stream and an aromatic-lean stream; and (ii) passing at least a
portion of the aromatics-lean stream to the second stage reforming stage.
5. The process of claim 4 wherein the aromatics separation between stages is accomplished
by a technique selected from extractive distillation, distillation, and flashing.
6. The process of claim 4 or claim 5 wherein the separation between stages produces three
streams, one of which is a C9+ aromatics-rich stream which is collected; a C5- stream which is also collected; and the remaining fraction which is sent to the second
stage reforming.
7. The process of any one of claims 1 to 6 wherein a C6 heartcut is separated from the feedstock before it enters a reforming zone and is
directed to the lead reactor of the second reforming stage.
8. The process of any one of claims 1 to 7 wherein the catalyst in each of the reforming
zones of the first stage is comprised of from 0.1 to 2 wt.% platinum, and from 0.1
to 3 wt.% of at least one metal selected from the group consisting of iridium, rhenium,
and tin.
1. Verfahren zum katalytischen Reformieren eines Kohlenwasserstoffreaktantstroms aus
dem Gasolinsiedebereich in Gegenwart von Wasserstoff in einer Reformierungsverfahrenseinheit,
die eine Vielzahl von in Reihe miteinander verbundenen Reformierungszonen umfaßt,
wobei jede der Reformierungszonen einen Reformierungskatalysator enthält, der mindestens
ein Edelmetall der Gruppe VIII auf einem feuerfesten Träger umfaßt, bei dem:
(a) der Reaktantstrom in einer ersten Refomierungsstufe reformiert wird, die eine
oder mehrere in Reihe miteinander verbundenen Reformierungszonen umfaßt, die einen
Festbettkatalysator enthalten, der ein oder mehrere Edelmetalle der Gruppe VIII auf
einem feuerfesten Träger umfaßt, wobei eine oder mehrere Reformierungszonen bei Reformierungsbedingungen
betrieben werden, die einen Manometerdruck von 100 bis 500 psig (6,896 bis 34,48 bar)
und ein H2:C5+ Molverhältnis im Bereich von 1 bis 10 umfassen, wodurch ein erster Austrittsmaterialstrom
erzeugt wird,
(b) der erste Austrittsmaterialstrom in eine Trennzone geführt wird, in der ein gasförmiger
wasserstoffreicher überwiegend C4-Kohlenwasserstoffstrom und ein überwiegend C5+-Austrittsmaterialstrom gebildet werden,
(c) ein Teil des gasförmigen wasserstoffreichen Stromes zu der ersten Reformierungsstufe
zurückgeführt wird,
(d) der C5+-Austrittsmaterialstrom mit dem verbleibenden Teil des gasförmigen wasserstoffreichen
Stromes in einer zweiten Reformierungsstufe reformiert wird, die bei einem Druck,
der mindestens 50 psi (3,45 bar) niedriger ist als derjenige der ersten Reformierungsstufe,
und bei einem H2:Öl-Molverhältnis von 0,5 bis 5,0 betrieben wird, wobei die zweite Reformierungsstufe
aus einer oder mehreren in Reihe miteinander verbundenen Reformierungszonen besteht,
die in einem kontinuierlichen Katalysatorregenerationsmodus mit sich bewegendem Bett
betrieben werden, wobei der Katalysator ein oder mehrere Edelmetalle der Gruppe VIII
auf im wesentlichen kugelförmigen feuerfesten Trägerteilchen umfaßt, wobei sich der
Katalysator kontinuierlich durch die Reformierungszone abwärtsbewegt, austritt und
in eine Regenerationszone geführt wird, in der er durch Ausbrennen mindestens eines
Teils von jeglichem angesammeltem Kohlenstoff regeneriert wird, und wobei der regenerierte
Katalysator kontinuierlich in eine oder mehrere Reformierungszonen zurückgeführt wird.
2. Verfahren nach Anspruch 1, bei dem der Katalysator in jeder der Refomierungszonen
der ersten Stufe 0,01 bis 5 Gew.-% Platin und 0,01 bis 5 Gew.-% mindestens eines Metalls
ausgewählt aus der Gruppe bestehend aus Iridium, Rhenium und Zinn umfaßt.
3. Verfahren nach Anspruch 1 oder Anspruch 2, bei dem (i) die erste Refomierungsstufe
zwei oder drei Festbettreformierungszonen enthält und (ii) die zweite Reformierungsstufe
ein oder zwei Reformierungszonen mit sich bewegendem Bett enthält, mit der Maßgabe,
daß, wenn zwei Refomierungszonen mit sich bewegendem Bett verwendet werden, sich der
Katalysator durch eine erste Reformierungszone mit sich bewegendem Bett abwärtsbewegt,
in eine zweite Refomierungszone mit sich bewegendem Bett geführt wird, wo er sich
durch die zweite Reformierungszone mit sich bewegendem Bett abwärtsbewegt, wird, dann
in eine Regenerierungszone geführt wird, wo jeglicher angesammelter Kohlenstoff abgebrannt
wird, woraufhin der regenerierte Katalysator zu der ersten Refomierungszone mit sich
bewegendem Bett zurückgeführt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem (i) Aromaten von mindestens einem
Teil des Reaktionsstromes der ersten Refomierungsstufe abgetrennt werden, wodurch
ein aromatenreicher Strom und ein aromatenarmer Strom gebildet werden, und (ii) mindestens
ein Teil des aromatenarmen Stroms zu der zweiten Refomierungsstufe geführt wird.
5. Verfahren nach Anspruch 4, bei dem die Aromatenabtrennung zwischen den Stufen durch
eine Technik bewirkt wird, die ausgewählt ist aus extraktiver Destillation, Destillation
und Schnellverdampfung (flashing).
6. Verfahren nach Anspruch 4 oder Anspruch 5, bei dem die Abtrennung zwischen den Stufen
drei Ströme erzeugt, wobei einer davon ein C9+ aromatenreicher Strom ist, der gesammelt wird, einer ein C5--Strom ist, der ebenfalls gesammelt wird, und einer die verbleibende Fraktion ist,
die zu der zweiten Refomierungsstufe zurückgeführt wird.
7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem ein C6-Herzschnitt aus dem Einsatzmaterial abgetrennt wird, bevor es in eine Refomierungszone
eintritt, und zu dem Führungsreaktor der zweiten Reformierungsstufe geführt wird.
8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem der Katalysator in jeder der Refomierungszonen
der ersten Stufe 0,1 bis 2 Gew.-% Platin und 0,1 bis 3 Gew.-% mindestens eines Metalls
ausgewählt aus der Gruppe bestehend aus Iridium, Rhenium und Zinn umfaßt.
1. Procédé de reformage catalytique d'un courant de réactif hydrocarboné qui se situe
dans la plage d'ébullition de l'essence en présence d'hydrogène dans une unité de
traitement de reformage comprenant une pluralité de zones de reformage reliées en
série, dans lequel chaque zone de reformage contient un catalyseur de reformage constitué
d'au moins un métal noble du groupe VIII sur un support réfractaire, ledit procédé
comprenant les étapes consistant:
(a) à reformer le courant de réactif dans un premier étage de reformage comprenant
une ou plusieurs zones de reformage reliées en série contenant un lit fixe de catalyseur
constitué d'un ou plusieurs métaux nobles du groupe VIII sur un support réfractaire,
la ou lesdites zones de reformage fonctionnant dans des conditions de reformage qui
comprennent une pression (manométrique) dans la plage de 6,896 à 34,48 bars (100 à
500 psig) et un rapport molaire H2:C5+ dans la plage de 1 à 10, produisant de la sorte un premier courant d'effluent,
(b) à faire passer ledit premier courant d'effluent dans une zone de séparation dans
laquelle on produit un courant gazeux d'hydrocarbure riche en hydrogène, principalement
en C4-, et un courant d'effluent principalement en C5+,
(c) à recycler une partie du courant gazeux riche en hydrogène audit premier étage
de reformage,
(d) à reformer le courant d'effluent en C5+ avec la partie restante du courant gazeux riche en hydrogène, dans un second étage
de reformage fonctionnant à une pression d'au moins 3,45 bars (50 psig) inférieure
à celle du premier étage de reformage et un rapport molaire H2:C5+ dans la plage de 0,5 à 5,0, ledit second étage de reformage comprenant une ou plusieurs
zones de reformage reliées en série qui fonctionnent en mode de régénération en continu
du catalyseur à lit mobile, ledit catalyseur comprenant un ou plusieurs métaux nobles
du groupe VIII sur des particules de support réfractaires sensiblement sphériques,
le catalyseur descendant en continu à travers la zone de reformage, sortant et passant
à une zone de régénération où il est régénéré en brûlant au moins une partie du carbone
qui y est éventuellement accumulé et le catalyseur régénéré étant recyclé en continu
vers la ou les zones de reformage.
2. Procédé selon la revendication 1, dans lequel le catalyseur dans chacune des zones
de reformage du premier étage est constitué de 0,01% à 5% en poids de platine et de
0,01% à 5% en poids d'au moins un métal choisi dans le groupe constitué de l'iridium,
du rhénium et de l'étain.
3. Procédé selon la revendication 1 ou 2, dans lequel (i) le premier étage de reformage
contient deux ou trois zones de reformage à lit fixe et (ii) le second étage de reformage
contient une ou deux zones de reformage à lit mobile à condition que, lorsqu'on utilise
deux zones de reformage à lit mobile, le catalyseur descende à travers une première
zone de reformage à lit mobile, passe à une seconde zone de reformage à lit mobile
à travers laquelle il descend et passe ensuite dans une zone de régénération où le
carbone qui y est éventuellement accumulé est brûlé, après quoi le catalyseur régénéré
est recyclé vers ladite première zone de reformage à lit mobile.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel (i) les aromatiques
sont séparés d'au moins une partie du courant de réaction du premier étage de reformage
en produisant ainsi un courant riche en aromatiques et un courant pauvre en aromatiques
et (ii) on fait passer au moins une partie du courant pauvre en aromatiques au second
étage de reformage.
5. Procédé selon la revendication 4, dans lequel la séparation des aromatiques entre
les étages se fait par une technique choisie parmi une distillation extractive, une
distillation et une distillation éclair.
6. Procédé selon la revendication 4 ou 5, dans lequel la séparation entre les étages
produit trois courants, à savoir un courant riche en aromatiques en C9+ qui est recueilli, un courant en C5- qui est également recueilli et la fraction restante qui est envoyée au second étage
de reformage.
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel une fraction
de coeur en C6 est séparée de la charge de départ avant qu'elle ne pénètre dans une zone de reformage
et est dirigée vers le réacteur principal du second étage de reformage.
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel le catalyseur
dans chacune des zones de reformage du premier étage comprend 0,1% à 2% en poids de
platine et 0,1% à 3% en poids d'au moins un métal choisi dans le groupe constitué
de l'iridium, du rhénium et de l'étain.