[0001] The fluidized catalytic cracking, or FCC, process is one of the work horses of modem
refineries.
[0002] In somewhat oversimplified terms, hot catalyst contacts a relatively heavy oil feed,
producing coked catalyst and cracked products. The coked catalyst is regenerated by
burning the coke from coked catalyst in a regenerator. The catalyst is heated during
the regeneration, because the coke bums. The hot regenerated catalyst is recycled
to contact more heavy oil feed.
[0003] In 1940's vintage FCC units, the heavy oil feed contacted the catalyst in a relatively
short transfer line which mixed the catalyst and oil together, and discharged the
catalyst/oil mixture into a dense bed reactor.
[0004] Gradually refiners learned that riser cracking (with a very short residence time,
typically on the order of under ten seconds) was more beneficial than dense bed cracking
(with catalyst/oil residence times on the order of 10 seconds - 60 seconds or more).
[0005] The desired reactions happened quickly in the catalyst riser. Some additional conversion
occurred in the dense bed reactor, but a significant amount of overcracking also occurred
in the dense bed and in the reactor vessel.
[0006] Modest conversions of feed to fuel oil and gasoline fractions occurred in the riser
reactor. Very modest incremental conversion of feed to lighter components was obtained
in the dense bed reactor, but there was also a significant amount of cracking of very
valuable gasoline and fuel oil components to coke and light gases.
[0007] Accordingly refiners have attempted to maximize riser cracking, and minimize dense
bed cracking. Generally this has been done by extending the catalyst riser and cutting
down on the amount of catalyst inventory in the relatively large vessel into which
the riser reactor discharged.
[0008] Some FCC units have attempted to practically eliminate dense bed cracking, by causing
the riser reactor to discharge into a rough cut cyclone, or to discharge down toward
the dense bed without agitating it, whereby substantial separation of cracked products
from deactivated catalyst can be quickly obtained. Such an approach is shown in U.S.
3,785.962.
[0009] Because of the number and size of FCC units in modem refiners, there has been tremendous
incentive to improve this process even more.
[0010] A profound improvement was the shift to the use of zeolite based catalyst which resulted
in a tremendous increase in catalyst activity.
[0011] Another development was the CO-afterbuming regenerator which resulted in more complete
combustion of coke to CO,, rather than CO, in the FCC regenerator.
[0012] U.S.
4,072,600 disclosed adding Pt, Pd, etc. to the circulating catalyst inventory to promote
afterbuming of CO to CO
2 in the FCC regenerator.
[0013] Despite the revolutionary changes which have improved the FCC process, we were not
satisfied that the process was operating at its maximum efficiency.
[0014] We discc- ed that other workers in this area overlooked one problem, or if they recognized
the problem, failed to see its solution.
[0015] The problem was the thermal cracking that occurred after riser cracking but before
the cracked products could be removed from the reactor vessel and subjected to conventional
product recovery techniques.
[0016] We discovered a way to significantly minimize the unnecessary losses of valuable
normally liquid products which occurred due to thermal cracking after riser cracking
had been completed, but before the cracked product could be removed from the reactor
and subjected to conventional product recovery.
[0017] Accordingly the present invention provides an improved FCC process wherein a conventional
fluidizable catalytic cracking catalyst and a hydrocarbon feed are charged to a reactor
riser at catalytic riser cracking conditions to form catalytically cracked vapor product
and spent catalyst which are discharged into a reactor vessel via a riser reactor
outlet connective with a separation means to produce a catalyst lean phase comprising
a majority of said cracked product, and a catalyst rich phase comprising a majority
of said spent catalyst, is discharged into a dense bed of catalyst maintained below
said riser outlet and said catalyst lean phase is discharged into said vessel and
then withdrawn from said vessel via a vessel outlet, the improvement comprising addition
of a quenching stream into said vessel above said dense bed of catalyst
[0018] Figure 1 shows an FCC riser reactor with quench steam ring.
[0019] Figure 2 shows a detail of an FCC reactor with a closed cyclone configuration and
quench steam ring installed.
[0021] Any conventional feed to an FCC unit can be used. Usually the feed to an FCC unit
comprises gas oils, vacuum gas oils, topped crudes, etc. Heavy feeds, such as tar
sands, shale oil, and asphaltic fractions may be used, if the unit can tolerate the
high metals concentrations and coking tendencies of these feeds. The present invention
is not the discovery of a new feed to an FCC unit, but a way to make better use of
feeds now used for FCC units.
[0023] Any catalyst suitable for use in an FCC unit can be used in the process of the present
invention. Preferably the catalyst is one of the many commercially available zeolite
based catalysts, but it is also possible to obtain benefits from practicing the present
invention when amorphous materials such as alumina, or amorphous silica/alumina are
used as the catalyst.
[0024] Especially preferred catalysts are rare earth exchanged Y zeolites in an amorphous
matrix. The catalyst may contain one or more of the following types of promoters.
1. CO oxidation promoters, such as disclosed in U.S. 4,072,600.
2. Metals passivation promoters, such as various antimony compounds.
3. Any other promoters hereafter developed for use in conjunction with FCC catalyst.
[0025] Neither the catalyst, nor any of the catalyst promoters, form any part of the present
invention. The present invention helps FCC units operating with conventional catalyst
to operate more efficiently.
FCC RISER REACTOR
[0026] Any conventional riser reactor, and riser reactor discharge means, can be used in
the present invention.
[0027] Preferably the riser reactor discharges directly into a rough cut cyclone, or other
separation means, whereby a very quick separation of cracked products from catalyst
may be contained.
[0028] If there's no room within the reactor to locate a rough cut cyclone on the discharge
of the riser reactor, it is preferred that the riser reactor discharge down into the
dense bed reactor, from a relatively high distance above the dense bed catalyst level.
This minimizes stirring up of the dense bed, and minimizes contact of cracked products/catalyst.
[0029] It is also acceptable, although not preferred, if the riser reactor discharges directly
into a dense bed of catalyst, either in a vertical up direction, or horizontally.
Such an operation tends to promote dense bed cracking, and should be avoided. Many
older FCC units were built at a time when dense bed cracking was more highly regarded,
and it is not possible to economically change the configuration of the units. It is
harder to see the benefits of the present invention in such units, because a lot of
hot catalyst is tossed about within the vessel containing the dense bed of catalyst,
minimizing the temperature quenching effect of the steam quench.
[0030] Integrating the above discussion, the preferred riser reactor provides a residence
time of less than 10 seconds, preferably on the order of 1-5 seconds, and it discharges
directly into a rough cut cyclone to effect rapid separation of cracked products from
catalyst.
[0031] The riser reactor may operate in upflow, or downflow, though an upflow riser reactor
is preferred because there is much more operating experience available for such a
unit
[0032] The riser reactor may actually be two or more reactors in series, or in parallel.
Although such riser reactor designs are contemplated for use herein, they form no
part of the present invention.
FCC DENSE BED REACTOR
[0033] As discussed above, the riser reactor discharges into a vessel designed to contain
a dense bed of catalyst. Conventional FCC dense bed reactor designs call for a rela-
tivety large vessel, usually several orders of magnitude larger in volume than the
riser reactor, which serves to collect spent catalyst in the lower portion of the
reactor. The spent catalyst is withdrawn from the bottom of the reactor, usually through
a stripper zone containing baffles, and removed from the reactor. Stripping steam
is added at the bottom of the reactor vessel to displace easily strippable hydrocarbons
from the spent catalyst, so that these etrip- pable hydrocarbons will not be burned
in the regenerator.
FCC REGENERATOR
[0034] Any conventional FCC regenerator may be used in conjunction with the present invention.
[0035] CO afterbuming regenerators are, in most situations, preferred as far as maximum
efficiency in the total FCC unit is concerned, however the present invention will
work equally well with CO afterbuming and non-CO afterbuming regenerators. The regenerator
is an essential portion of an FCC unit, but the regenerator section, by itself, forms
no portion of the present invention.
[0036] An especially effective regenerator design is a stacked regenerator with a first
dense bed, or coke combustor, a dilute phase transport riser and a second dense bed
of hot regenerated catalyst maintained generally above the coke combustor. Some recycle
of hot regenerated catalyst to the coke combustor generally improves operation in
the coke combustor.
REACTOR QUENCH
[0037] Preferably one or more quench means are disposed within the reactor vessel into which
the riser reactor discharges. Steam is the preferred quenching medium. Steam is preferably
admitted via a radially disposed steam injection ring disposed just above the dense
bed of catalyst
[0038] The function of the steam quench is twofold. It reduces the temperature of the cracked
products in the vapor phase above the dense bed of catalyst. It also displaces the
cracked hydrocarbons from the reactor vessel, thereby decreasing the residence time
of these materials in the reactor vessel. The combination of these two effects, reduction
in temperature and reduction in vapor residence time, significantly reduces the amount
of thermal cracking that occurs in the riser reactor.
[0039] If the steam quench rings are located too near the surface of the dense bed of catalyst,
there is a risk that the hot catalyst will be stirred up by the steam injection, which
will result in some catalyst displacement into the dilute phase, leading to overcracking
of cracked products, and leading to increased temperatures in this zone. The generally
small amounts of steam quench that are added are effective to reduce the temperature
and residence time of cracked products, but we prefer not to add enough steam to reduce
the temperature of the hot catalyst. This is largely a matter of economics, to significantly
cool the hot catalyst would require relatively large amounts of steam, and would,
in most instances, simply waste heat.
[0040] As the steam quench point rises in the reactor vessel, the effectiveness of the steam
quench gradually diminishes.
[0041] It may be beneficial to add steam quench at the very outlet of the reactor. There
would be no reduction in temperature or residence time of cracked vapors in the reactor,
but there would be a quenching effect, and a reduction of residence time, in the transfer
line going to downstream product recovery units.
[0042] The amount of steam quench injected, and the precise location of the steam quench
injection point within the vessel containing the dense bed of spent catalyst, will
determine the change in residence time of cracked vapors within the reactor. The temperature,
and amount of steam qt!r - sh will determine the temperature change of cracked product
within the reactor.
[0043] The temperature of the steam will have a significant effect on the quenching effect,
or temperature reduction of cracked products. It is also possible to simply add water
and let the water vaporize within the reactor, or provide enough surface area in the
steam quench ring so that the water will vaporize and become steam before entering
the reactor. This would give maximum cooling per weight of water added, the cooling
effect being vaporization of water to steam, followed by an increase in sensible heat
of the steam produced.
[0044] To minimize corrosion problems, and possibilities of temperature shock within the
reaction zone, it is usually preferred to simply add some low grade steam, such as
450 kPa (50 psig) steam which is usually a very cheap and readily available commodity
within a refinery.
[0045] Addition of a vaporizable liquid hydrocarbon is also possible, with naphtha and gas
oil or distillate fractions being preferred. These all vaporize, and are believed
at least moderately resistant to thermal cracking.
[0046] Because the optimum amount of quench will vary with each refinery unit's configuration,
and indeed with different chargestocks and operating conditions, it is not possible
to specify one unique quantity and temperature of quench for best results. Instead
some general guidelines can be given, with the following discussion focusing the steam
addition.
[0047] Improved results can be obtained when steam, or water, equivalent to about 0.1-20
wt % of the cracked hydrocarbon vapors is added to the steam quench means. Preferably,
an amount of steam equal to 0.5-5 wt% of the cracked vapors is added.
[0048] In some situations, addition of this much steam will have little effect upon the
temperature in the dilute phase, above the dense bed of catalyst in the reactor vessel,
but even here significant operating improvements can be obtained. Whenever the riser
reactor discharges into an open cyclone, there is a significant amount of hydrocarbon
vapor that remains a long time in the dilute phase above the dense bed of spent catalyst.
There is also some, 1-2% hot catalyst that finds its way into the dilute phase, and
this hot catalyst tends to heat up the dilute phase above the dense bed. In these
operations it is believed that the primary benefit of the present invention is from
reduced residence time of hydrocarbon products in the dilute phase, rather than from
any temperature drop, although the small drop in temperature that occurs in such an
operation is certainly beneficial. It is also possible that some of the beneficial
effect of our steam quench operation is one additional stage of stripping of catalyst,
but this is not believed to be a significant part of the improved results seen, because
well over 90 percent of the catalyst simply bypasses our steam quench ring and never
sees the steam injection.
[0049] The most noticeable improvement in operation, and the greatest drop in temperature
of the hydrocarbon phase above the dense bed of spent catalyst, occurs when closed
cyclones are used.
[0050] In this type of operation, the riser reactor discharges into a primary cyclone, which
makes a rough, but fairly effective, separation of catalyst from cracked products.
The vapor from the primary cyclone is discharged directly into a secondary cyclone
which is able to effect a far more complete separation of catalyst from cracked products
than could be achieved in the rough cut cyclone attached directly to the riser reactor
outlet
[0051] In such a design, with dosed cyclones, relatively minor amounts of steam injection
result in significant decreases in reactor temperature, typically 10-20 times as great
as those obtained in an open cyclone system. Despite almost an order of magnitude
or more greater drop in temperature of dilute phase vapors above the dense bed of
catalyst, the results as far as increased gasoline and light fuel oil make, are only
slightly better than those achieved in the open cyclone case. This is probably because
only a small portion of the vapors remain in the reactor vessel with the closed cyclone
( 3 wt%).
[0052] The extent of undesirable thermal cracking that goes on in a reactor may be estimated
by calculating the residence time in the reactor at a given temperature. These two
numbers can be used to devise an ERT or Equivalent Reaction Time at 427°C (800°F).
More details about ERT are provided in U.S. 4,379,747 and U.S. 4,428,824. Another
way of evaluating relative reaction velocities in thermal cracking is to compare S.F.
or Soaking Factors. By definition, the ERT and SF are
1.0 at 427°C (800°F). As the temperature increases, the reaction rate increases, to
2.0 at 439°C (822°F), and so on.
[0053] The amount of thermal cracking will be cut about in half by reducing the residence
time of the catalytically cracked product by one half, or by reducing the vapor temperature
from 439 to 427°C (822 to 800°F), or some combination of these.
[0054] When closed cyclones are used, the same amount of steam injection profoundly reduces
temperature and ERT, reducing ERT by more than 50%.
[0055] When open cyclones are used, much smaller declines in ERT may be expected; usually
on the order of 3 - 50% decreases in ERT will be experienced. This is much less reduction
in thermal cracking severity, but 10 to 20 times the material is involved, as compared
to the closed cyclone case.
[0056] Regardless of the cyclone configuration used, the amount of quench added should be
sufficient to reduce thermal cracking enough to increase the yield of gasoline and
light fuel oil products at least 1/2%, and preferably 1 to 2%, or more.
[0057] The present invention may be better understood by reviewing it in conjunction with
the drawing.
[0058] The drawing is schematic, many details such as instrumentation, etc. have been left
out
[0059] In Figure 1, a mixture of hot regenerated catalyst, from a catalyst regenerator not
shown, and fresh feed is mixed together and passed up through reactor riser 4. The
catalyst oil mixture leaves reactor riser 4, and enters primary cyclone 2 which effects
a rough separation of spent catalyst from cracked products. Most of the spent catalyst
is discharged from primary cyclone 2 via dipleg 12 and flapper valve 11. Cracked vapors
leave the top of cyclone 2 via outlet 3 and enter into the dilute phase 15 within
reactor 1.
[0060] The terminology used in the specification is consistent with terminology used in
modem refineries, however it should be pointed out that what is referred to as reactor
riser 4 is in actuality the reactor where well over 90 percent of the desired catalytic
cracking reactions occur. Ideally,
100 percent of the reactions would take place in reactor riser 4, and no reaction whatever
would take place in reactor
1. In time, refiners may revise their vocabulary to refer to riser 4 as the reactor,
and vessel 1 as a spent catalyst/cracked product separation means, but such usage
would be confusing to those skilled in the FCC arts.
[0061] Vapors leaving primary cyclone 2 enter into the dilute space above the top of dense
bed of catalyst 17. Dense bed 20, with upper surface or interface level 17 is the
collection of catalyst from the diplegs of the cyclones within reactor 1. The dense
bed/dilute phase interface 17 may be below the catalyst diplegs, as shown in the drawing,
or the dense bed level may be raised, or the diplegs extended, so that the diplegs
are immersed within the dense bed of catalyst 20.
[0062] Cracked product in dilute space 15, along with relatively minor amounts of catalyst
entrained in the vapor phase enter the secondary cyclone means 6 via inlet 5. Catalyst
fines are withdrawn via dipleg 16 and discharged into the dense bed of catalyst, although
only the upper portion of the dipleg is shown in this drawing.
[0063] Cracked product vapors are removed via vapor outlet 7 from cyclone 6 and discharged
into third stage separation means 8, another cyclone. Catalyst removed from the third
stage cyclone is removed via dipleg 18 and discharged through flapper vaive 19 into
dense bed 20 of catalyst at the bottom of reactor 1.
[0064] Catalytically cracked products are removed from reactor 1 via lines 9 and 13 into
reactor outlet plenum 14 and then sent via line 10 to product recovery means not shown.
To simplify the drawing, only a single cyclone is shown for primary cyclone 2, secondary
cyclone 6 and third stage cyclone 8. In actuality, there usually would be a plurality
of primary, secondary, and third stage cyclones. The second inlet line 13 to plenum
14 is intended to show that other third stage cyclones will be present
[0065] The spent catalyst which collects as dense bed 20 in the bottom of reactor 1 is subjected
to stripping to remove easily strippable hydrocarbon vapors from the spent catalyst
before it is sent to a catalyst regenerator, not shown. This steam stripping of spent
catalyst, which is conventional, is conducted at reactor stripper 21. A steam supply,
shown as line 30, admits steam via either line 22 and/or 24 to lower and upper stripper
steam rings, respectively.
[0066] Steam is also admitted via line 26 to quench-steam ring 27, located above the interface
level 17 of dense bed of catalyst 20. Only a single quench steam ring is shown in
the drawing, extending radially around the reactor, it is also possible to have multiple
quench steam rings at different elevations within the reactor vessel 1, or to use
steam injection means other than a ring. One or more stab-in steam spargers could
be used to add steam, or steam may be injected to counter any naturally occurring
swirl of catalyst that occurs at the bottom of the reactor.
[0067] Steam quench should be conducted so as to minimize disruption of dense bed of catalyst
20. For this reason, quench steam injection should always be at, or preferably somewhat
above, the interface 17 between dilute phase 15 and dense bed 20.
[0068] The configuration shown in Figure 1 is referred to as an open cyclone configuration,
because there is no direct connection between primary cyclone 2 and secondary cyclone
6.
[0069] It is also possible, and preferable, to operate with closed cyclones, in which case
inlet 5 to cyclone 6 would resemble an inverted funnel which was radially aligned
with, and above outlet. 3 of primary cyclone 2, as shown in Figure 2. Such a configuration
is not, strictly speaking, "closed", because it is still possible, and very desirable,
for cracked hydrocarbon products, and quench steam, to enter inlet 5 in the annular
space between outlet 3 and inlet 5. There has to be some way provided of allowing
cracked vapor and quench steam and stripping steam to eventually enter the outlet
plenum 14, and the closed cyclone modification described above works very well in
this service. When operating with a closed cyclone, it is beneficial io immerse dipleg
12 about 50 cm past the dense bed/dilute phase interface 17. This minimizes leakage
of vapors down dipleg 12, as the catalyst seals the outlet of dipleg 12.
[0070] A characteristic of "closed cyclone" configuration is that 90% of the cracked vapor
product will pass from the primary cyclone outlet and enter the secondary cyclone
inlet in less than 1 second, preferably in less than 1/2 second.
[0071] Although not shown in the drawing, it is also possible to eliminate entirely the
primary cyclone 3, and merely have the riser reactor discharge down towards interface
17, from a distance 3-10 meters above it. This does only a mediocre job of separating
catalyst from cracked vapors, but in many existing reactors, it's not possible to
support primary cyclones 2 at the reactor riser outlet, either because of lack of
strength or lack of room. In such circumstances, a downward discharge of spent catalyst/cracked
product from 3-10 meters above the dense bed interface provides a way to achieve some
semblance of quick quench of the riser cracking reaction. If such an approach is taken,
it may be desirable to use multiple quench steam rings. Quench steam ring 27 shown
in the drawing would reduce the residence time of cracked products in space 15, but
would do little or nothing towards reducing the temperature of the cracked products,
because of the large amount of hot spent catalyst present. In such a circumstance,
it may be beneficial to move the quench steam ring to an elevation equal to, or slightly
above the reactor riser outlet, so that steam quench will have a noticeable cooling
effect on reactor vapors. In some circumstances, a combination of steam quench via
quench ring 27 shown in the drawing and another quench ring located above the riser
reactor outlet, and not shown in the drawing, would be beneficial.
[0072] The two illustrative embodiments which follow do not represent commercial or laboratory
tests. They are based on computer simulations of commercial operation, and are believed
to be accurate predictors of what will happen in commercial operation.
[0074] Based upon the above assumptions, and using our computer simulation of the FCC process,
we calculated the effect that would be obtained by adding 0.567 Kg/sec (4500 pounds
per hour) of quench steam, equivalent to about 1.125 wt % of the hydrocarbon feed
to the unit.

[0075] As can be seen from Table III, there was a significant increase, of 0.5 wt %, in
production of gasoline and light fuel oil. Gasoline production went from 39.5 wt%
of feed to 39.7 wt% of feed. Light Fuel Oil increased from 28.5 wt% to 28.8 wt%.
[0076] There would be no significant change in the octane number of the gasoline, depending
on the O.N. of catalytically cracked gasoline versus thermally cracked gasoline. It
is possible that the ocanb may actually drop a little.
[0077] In this example, the amount of steam quench added did little towards reducing the
reactor vessel temperature, resulting in a decrease of only 1.7°C (3°F) from 535.0
° C (995°F) to 533.3°C (992°F). This change in temperature reduces the ERT from 104
to 100. Here reactor vessel temperature refers to the vapor outlet temperature, measured
at the top of the reactor. The reason the reactor vessel temperature did not change
much was because in the open cyclone configuration, corresponding roughly to the one
shown in the drawing, the steam is in contact with significant amounts of hydrocarbon
exiting the vessel and some catalyst.
[0078] The reduction in vapor residence time in the dilute phase portion of reactor vessel
1 is estimated to be about 10-15%, or a reduction of about 4 to 6 seconds residence
time. A unit weight of water occupies almost 10 times the volume uf a unit weight
of acked product in the reactor, based on 18 mw for water and an assumed average mw
of 180 for cracked product.
[0079] This exercise was repeated, but based upon a slightly different set of assumptions.
In this simulation, a closed cyclone configuration was used, wherein more than 97%
of the vapors from the primary cyclone outlet went directly into the secondary cyclone
inlet Quench steam rate was 0.567 Kg/sec (4500 pounds per hour), equivalent to 1.125
wt % on reactor hydrocarbon feed.
[0080] Results of this computer simulation are reported in Table IV.

[0081] In this instance, reactor vessel temperature refers to the temperature at the top
of the reactor vessel, which is not the same thing as the temperature of the vapor
leaving the reactor. The vapor leaving the unquenched reactor would have a temperature
of about 535.0°C (995°F). The supercooling of the reactor vessel dilute phase temperature
by quench steam was due to the fact that the closed cyclone configuration resulted
ir significantly less cked vapor and entrained catalyst being discharged into the
dilute phase within reactor vessel 1. The quench steam was far more effective in cooling
down this greatly reduced weight of material, in the dosed cyclone configuration case,
than when the quench steam was being inundated by vast amounts of cracked vapors and
spent catalyst, as in the open cyclone configuration discussed in conjunction with
Table III.
[0082] The reduction in severity, due to temperature change alone, is equal to 104/43.6,
for reduction in thermal cracking of almost 60%.
[0083] The 1/2 wt % increase in valuable products is significant, because on a commercially
sized unit this incremental yield translates into a projected increase in production
of gasoline and light fuel oil of almost 15,000 m
3 (4 million gallons) per year, based on a 0.0823 m
3/sec (45,000 BPD) FCC unit The cost of adding a steam quench ring, and using low grade
refinery steam, is insignificant in comparison to the increased production of gasoline
and light fuel oil that can be obtained.
[0084] If we were designing an FCC unit today, and wanted to incorporate steam quench, we
would use a riser reactor with a closed cyclone configuration, i.e. one in which the
riser reactor discharged directly into a primary cyclone separator. The vapor outlet
from the primary cyclone separator would be closely connected with the inlet to a
secondary cyclone separator, so that most of the vapor phase would very quickly leave
the reactor vessel. Steam quench would be added to a steam quench ring located about
1 meter above the top of the dense bed of catalyst in the reactor. Steam quench, equivalent
to 1 wt % of feed, would be added. Steam source would be 450 kPa (50 psig) steam from
a refinery steam line.