BACKGROUND OF THE INVENTION
[0001] This invention relates to catalytic cracking and, more particularly, to a process
and system for increasing the yield of valuable liquids in a catalytic cracking unit.
[0002] Catalytic cracking of oil is an important refinery process which is used to produce
gasoline and other hydrocarbons. During catalytic cracking, the feedstock, which is
generally a cut or fraction of crude oil, is cracked in a reactor under catalytic
cracking temperatures and pressures in the presence of a catalyst to produce more
valuable, lower molecular weight hydrocarbons. Gas oil is usually used as a feedstock
in catalytic cracking. Gas oil feedstocks typically contain from 55% to 80% gas oil
by volume having a boiling range from about 650°F (343°C) to about 1000°F (538°C)
and less than 1% RAMS carbon by weight. Gas oil feedstocks also typically contain
less than 5% by volume naphtha and lighter hydrocarbons having a boiling temperature
below 430°F (221°C) from 10% to 30% by volume diesel and kerosene having a boiling
range from about 430°F (221°C) to about 650°F (343°C), and less than 10% by volume
resid oil having a boiling temperature above 1000°F (538°C). Resid oil is sometimes
present in greater concentrations or added to the gas oil feedstock.
[0003] In conventional fluid catalytic cracking units (FCCU), the hot products from the
riser reactor continue to undergo thermal cracking reactions above 900°F (482°C) downstream
of the riser reactor. These thermal cracking reactions degrade the products, reduce
yields, and make excess light gases which often unduly limit the production capability
of the catalytic cracking unit.
[0004] Furthermore, while it is often desirable to operate a riser reactor at higher temperatures,
such as at 1025°F (552°C) or higher, to increase gasoline octane and oil and resid
conversion, such high temperature cracking have substantially increased the production
of ethane and lighter fuel gas. This dramatic increase of fuel gas production can
create an imbalance in the refinery fuel gas system. It may also limit the capacity
of those FCCUs which have insufficient gas compression capability to handle the increased
load. Therefore, despite incentives for increased gasoline and octane production,
riser temperatures have sometimes been reduced.
[0005] Operation at higher cracking temperatures produce naphthas which are less stable
and are more prone to undergo undesired oxidation reactions which form gums. Prior
methods for maintaining the stability of cracked naphthas and for maintaining the
stability of gasolines containing cracked naphthas have included: 1) addition of antioxidant
chemicals such as phenylene diamines or hindered phenols; 2) manipulation of the operating
variables of the cracking process, such as lowering the cracking temperature and/or
limiting the amount of resid; or 3) limiting the amount of cracked naphtha blended
into the finished gasoline.
[0006] Typifying some of the many prior art catalytic crackers, regenerators, catalysts,
equipment and refinery processes are those shown in U.S. Patents: 2,240,160; 2,382,270;
2,382,382; 2,398,739; 2,398,759; 2,414,002; 2,422,501; 2,425,849; 2,436,927; 2,458,862;
2,669,591; 2,827,422; 2,884,303; 2,901,418; 2,981,676; 2,985,584; 3,004,926; 3,039,953;
3,290,405; 3,338,821; 3,351,548; 3,364,136; 3,513,087; 3,563,911; 3,593,968; 3,661,800;
3,676,519; 3,692,667; 3,838,036; 3,844,973; 3,850,742; 3,886,060; 3,907,661; 3,909,392;
4,043,899; 4,218,300; 4,325,817; 4,331,533; 4,332,674; 4,341,623; 4,341,660; 4,375,021;
4,446,009; 4,478,708; 4,552,645; 4,695,370; 4,764,268; 4,814,067; 4,824,557; 4,859,310;
and European Patent Application Nos. 83307095.6 (publication no. EPO 113 180 A2),
85307242.9 (publication no. EPO 180 355 A2), and 88309278.5 (publication no. EPO 311
375 A1). These prior art catalytic crackers, regenerators, catalysts, equipment, and
refinery processes have met with varying degrees of success.
[0007] It is, therefore, desirable to provide an improved process and system to increase
the yield of gasoline (naphtha) in catalytic cracking units and which improves the
stability of gasoline (petrol) which contain these naphthas.
[0008] At a direction of the European Examiner, reference is made to the following documents:
i) US-A-2906695 refers to a catalytic cracking process best suited for conversion
of heavy hydrocarbon fractions that produce large quantities of coke upon cracking.
The feed is heated in a vaporization zone and, upon leaving the vaporization zone,
is caused to rotate strongly and then passes upwardly through a conical curtain of
hotter particulates into a cracking zone where the temperature of the vapors is 1250°F-1800°F
(677°C-982°C). The centrifugal action is relied upon to separate the particulates
into a chamber surrounding the cracking zone, and injected into the vapors passing
out of an outlet at the top of the chamber is a quench consisting of cooled hydrocarbon
oil, water, cooled particulates or gases. It is a high temperature short time cracking
process.
ii) EP-A-100182 discloses a catalytic cracking process and apparatus in which a cyclone
separator for separating entrained catalyst is connected to the upper end of a riser
reactor by a first passageway which extends horizontally from the riser reactor, this
passageway being adapted to separate catalyst and direct it into a collecting and
stripping vessel, and a second, vertical restricted passageway. These passageways
and the cyclone separator provide a direct path for the vapors out of the elevated
temperature zone so that they may be quenched in the main fractionator of the processing
unit. However, the restricted passageway may include steam or water coils for indirect
cooling, or means to inject liquid or gaseous quench for direct cooling.
iii) EP-A-0381870 (Article 54(3) reference) discloses a catalytic cracking process
for production of olefins and aromatics. The hydrocarbon feedstock and acidic catalyst
solids pass downwardly through a vertical reactor, and enter a catalyst separator
having a bottom outlet connected to a solids stripper and a top outlet for vapours
connected to a cyclone separator for separation of entrained catalyst. Upstream of
the cyclone separator is an in-line quench, suitable quench materials being cold solids,
water, steam, light hydrocarbons and recycle oils, or quenching by passing the product
over a catalyst bed. The residence time between introduction of feedstock to the reactor
and quench is 0.1 to 2.0 seconds, in conjunction with the acidic catalyst is said
to improve olefin yields.
SUMMARY OF THE INVENTION
[0009] An improved catalytic cracking process and unit are provided which are effective,
efficient, and economically attractive.
[0010] The novel catalytic cracking process comprises catalytically cracking feed oil, such
as gas oil, hydrotreated oil, and/or resid oil, in a reactor of a catalytic cracking
unit (FCCU) in the presence of a cracking catalyst to produce a catalytically cracked,
effluent product stream of upgraded oil, substantially separating said catalyst from
said upgraded oil, and quenching said upgraded oil with a quench comprising at least
one member selected from the group consisting of light catalytic cycle oil, heavy
catalytic cycle oil, heavy catalytic naphtha, kerosene, coker distillates, light coker
gas oil, hydrotreated distillate, fresh unprocessed virgin gas oil, and fresh unprocessed
virgin naphtha, the quench being injected into the stream in an amount ranging from
2% to 20% by volume per barrel of feed oil.
[0011] Quenching the upgraded oil stream substantially immediately after catalyst separation
makes it possible to increase the yield of naphtha and gasoline (petrol) and produce
more stable gasoline. Rapid quenching also attains a desirable shift in coke make
and selectivity.
[0012] The quench has a volumetric expansion on vaporization substantially less than water
and steam. In the preferred form, the quench comprises a hydrocarbon stream which
has been previously cracked or otherwise processed to remove the most reactive species.
Desirably, the quench should have low thermal reactivity. Previously cracked hydrocarbons
are very desirable because they are less reactive to thermal quenching than fresh
unprocessed virgin feedstocks and hydrotreated stocks.
[0013] To this end, the quench comprises kerosene, light coker gas oil, coke still (coker)
distillates (CSD), hydrotreated distillate, or fresh unprocessed virgin feedstocks,
such as virgin gas oil, heavy virgin naphtha, light virgin naphtha, but preferably
comprises light catalytic cycle oil (LCCO or LCO), heavy catalytic cycle oil (HCCO
or HCO), or heavy catalytic naphtha (HCN), or any combination thereof. LCCO boils
at a lower temperature than HCCO but they have about the same heat of vaporization.
For best results, the quench comprises LCCO which has a greater molecular weight than
water. HCCO, however, is also very useful as a quench and less expensive than LCCO.
[0014] Use of steam of water as a quench is not within the ambit of the invention and they
are generally not desirable as a quench, because they: expand a lot on vaporization,
take up a lot of reactor volume, expand in overhead lines, cause pressure disruption,
disturb catalyst circulation, adversely affect cyclone operation, and produce substantial
quantities of polluted water which have to be purified. Excessive quantities of steam
are also required in steam quenching.
[0015] Light naphtha (light virgin naphtha, light catalytic naphtha, light coker naphtha,
etc.) is also not generally desirable as a quench because it occupies too much volume
in the reactor. Furthermore, light naphtha is a gasoline blending product and it is
not desirable to crack the light naphtha into less valuable hydrocarbons.
[0016] Decanted oil (DCO) is not generally desirable as a quench because it has a tendency
to coke. Catalyst in the DCO can also erode the interior reactor walls and lines.
[0017] Resid is further not desirable as a quench because it has a tendency to coke and
plug up lines.
[0018] Liquid hydrocarbon quenches are preferred over gas quenches to attain the benefit
of the heat of vaporization of the liquid quench. The liquid quench is injected into
the product stream in an amount ranging from 2% to 20%, and preferably from 5% to
15% of the volume flow rate of feed oil for best results. Advantageously, quenching
decreases the temperature of the product stream and minimizes thermal cracking. Quenching
can also increase the conversion of feed oil to upgraded oil and can increase the
octane of the gasoline.
[0019] Kerosene, coker gas oil, and hydrotreated distillates are less advantageous as a
quench than are LCCO and HCCO. Liquid nitrogen can be useful as a quench but is very
expensive and has an undesirable volumetric expansion.
[0020] LCCO and HCCO have a high capacity to absorb heat, enhance operations, and do not
materially increase operating utility, maintenance, and waste treatment costs. LCCO
and HCCO provide excellent quenches because they are readily available in refineries,
economical, stable, have low volume expansion, provide recoverable heat removal and
have a low tendency to form coke. Quenching with cycle oil can decrease the amount
of coke produced. Cycle oil quenching also permits high temperature cracking without
loss of more valuable hydrocarbons, and without damaging internal cyclones, plenum,
or refractory walls. Desirably, cycle oil quenching, substantially decreases fuel
gas production.
[0021] In one embodiment of the process, the coked catalyst is separated from the upgraded
oil by gross separation in a vapor catalyst separator, such as in a rough cut cyclone,
and the upgraded oil is immediately quenched to decrease thermal cracking of the upgraded
oil to less valuable hydrocarbon products and light hydrocarbon gases. Desirably,
the quenching occurs downstream of a riser reactor and the vapor product outlet (exit)
of the rough cut cyclone of the catalytic cracking unit. It is more efficient and
economical to add the quench to the catalytic cracked oil after gross separation of
the catalyst from the oil. Required quench volumes and pumping costs are also decreased.
[0022] In one of the illustrated embodiments, quenching occurs upstream of the disengaging
and stripping vessel. In one form of this application, the catalytic cracking unit
has an external rough cut cyclone positioned between the riser reactor and the disengaging
and stripper vessel and the quench is injected immediately downstream of the vapor
(product) exit of the external rough cut cyclone.
[0023] In other illustrated embodiments, the catalytic cracking unit has a disengaging vessel
(disengager) with an internal rough cut separator and the quench is injected into
the disengager immediately downstream and in proximity to the vapor (product) exit(s)
of the internal rough cut separator. The internal rough cut separator can comprise
an internal cyclone or an inverted can separator. Ballistic separator and other inertia
separators can also be used.
[0024] Advantageously, with quenching, the selectivity of coke can be decreased and less
coke can be produced in the dilute phase portion of the disengaging and stripping
vessel. Spent coked catalyst is regenerated in a regenerator and is recycled to the
riser reactor. Desirably, during the novel quenching process the regeneration temperature
of the regenerator is decreased. In the preferred mode, the regenerator is operated
in full CO (carbon monoxide) combustion whereby the coked catalyst is regenerated
in the presence of a combustion-supporting gas, such as air, comprising excess molecular
oxygen in an amount greater than the stoichiometric amount required to completely
combust the coke on the coked catalyst to carbon dioxide. The regenerator can also
be operated in partial CO burn.
[0025] There is also provided in accordance with the invention a catalytic cracking unit
comprising
an upright elongated riser reactor for or catalytically cracking feed oil in the
presence of a cracking catalyst to produce an upgraded effluent product stream of
catalytically cracked oil leaving coked catalyst, said riser reactor having an upper
portion and a lower portion;
an external rough cut separator connected to and communicating with said upper
portion of said riser reactor and being spaced from, positioned about and at a substantially
similar elevation as said upper portion of said riser reactor for making a gross separation
of said coked catalyst from said catalytically cracked oil;
an upright disengaging vessel for substantially disengaging and separating a substantial
amount of remaining coked catalyst from said catalytically cracked oil, said disengaging
vessel having an upper dilute phase zone with at least one internal separator, a lower
dense phase zone, and a stripping section providing a stripper;
product line extending between and connecting said external separator and said
upper diluate phase portion of said vessel;
a spent catalyst line extending between and connecting said external separator
and said dense phase portion of said disengaging vessel;
a regenerator comprising a vessel an upright elongated lift pipe for transporting
coked catalyst to regenerator, an air injector communicating with said lift pipe for
injecting air and facilitating combustion of said coked catalyst, and a regenerated
catalyst line connected to said riser reactor for conveying regenerated catalyst to
said riser reactor; and a cycle oil quench injection line connected to and communicating
with said input line for injecting a quench comprising cycle oil selected from the
group consisting of light catalytic cycle oil and heavy catalytic cycle oil, into
said catalytically cracked oil after said catalytically cracked oil has exited said
external separator downstream of said riser reactor and has been grossly separated
from said catalyst and before said catalytically cracked oil enters said disengaging
vessel for enhancing the yield of naphtha and substantially decreasing thermal cracking
of said product stream of oil, said cycle oil quench line including a substantial
vertical light cycle oil injector for injecting said quench substantially vertically
downwardly into said input line or being at an angle of inclination ranging from about
15 degrees to about 45 degrees relative to a vertical reference line for increasing
mixing of said quench with said products.
[0026] Another form of catalytic cracking unit according to the invention comprises
an upright elongated riser reactor for catalytically cracking feed oil in the presence
of a cracking catalyst to produce an upgraded effluent product stream of catalytically
cracked oil leaving coked catalyst, said riser reactor having an upper portion and
a lower portion;
an upright disengaging vessel communicating with said riser reactor for substantially
disengaging and separating a substantial amount of coked catalyst from said catalytically
cracked oil, said disengaging vessel having an upper dilute phase zone with at least
one internal cyclone, a lower dense phase zone, and a stripping section providing
a stripper;
an internal gross cut separator positioned in said dilute phase zone of said disengaging
vessel for making a gross separation of said coked catalyst from said catalytically
cracked oil, said internal gross cut separator defining a vapor port providing an
oil outlet and having a lower portion providing a catalyst outlet;
a regenerator comprising a vessel, an upright elongated lift pipe for transporting
coked catalyst from said disengaging vessel to said regenerator, an air injector communicating
with said lift pipe for injecting air and facilitating combustion of said coked catalyst,
and a regenerated catalyst line connected to said riser reactor for conveying regenerated
catalyst to said riser reactor; and
at least one cycle oil quench injection line extending into the interior of said
disengaging vessel and substantially aligned in registration with said oil outlet
of said internal gross cut separator for injecting a quench comprising cycle oil selected
from the group consisting of light catalytic cycle oil and heavy catalytic cycle oil,
into said catalytically cracked oil after said catalytically cracked oil has exited
said oil outlet of said internal gross cut separator and has been grossly separated
from said catalyst for substantially enhancing the yield of naphtha and substantially
decreasing thermal cracking of said product stream of oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027]
Figure 1 is a schematic flow diagram of a catalytic cracking unit with an external
cyclone;
Figure 2 is a schematic flow diagram of another catalytic cracking unit with an external
cyclone;
Figure 3 is a schematic flow diagram of part of an oil refinery;
Figure 4 is a schematic flow diagram of another part of the oil refinery;
Figure 5 is a schematic flow diagram of a coker unit;
Figure 6 is a schematic flow diagram of a catalytic cracking unit; and
Figures 7 and 8 are charts of product temperature for various amounts of quenches;
Figure 9 is a chart of quench volume to product volume;
Figures 10 and 11 are charts of the effects of initial quench at different catalytic
cracking units;
Figure 12 is a schematic flow diagram of a catalytic cracking unit with an internal
rough cut separator;
Figure 13 is a cross-sectional view of the disengager of Figure 12 taken substantially
along lines 13-13 of Figure 12;
Figure 14 is an enlarged fragmentary cross-sectional view of a disengager with an
inverted can and quench lines, taken substantially along lines 14-14 of Figure 15;
Figure 15 is a schematic flow diagram of a catalytic cracking unit with a center riser
reactor and an internal rough cut separator comprising an inverted can; and
Figure 16 is a schematic flow diagram of another catalytic cracking unit with an internal
rough cut separator.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] In refining, unrefined, raw, whole crude oil (petroleum) is withdrawn from an aboveground
storage tank 10 (Figure 3) by a pump 12 and pumped through feed line 14 into one or
more desalters 16 to remove particulates, such as sand, salt, and metals, from the
oil. The desalted oil is fed through furnace inlet line 18 into a pipestill furnace
20 where it is heated to a temperature, such as to 750°F (399°C) at a pressure ranging
from 125 to 200 psi (863 to 1380 kPa). The heated oil is removed from the furnace
through exit line 22 by a pump 24 and pumped through a feed line 25 to a primary distillation
tower 26.
[0029] The heated oil enters the flash zone of the primary atmospheric distillation tower,
pipestill, or crude oil unit 26 before proceeding to its upper rectifier section or
the lower stripper section. The primary tower is preferably operated at a pressure
less than 60 psi (414 kPa). In the primary tower, the heated oil is separated into
fractions of wet gas, light naphtha, intermediate naphtha, heavy naphtha, kerosene,
virgin gas oil, and primary reduced crude. A portion of the wet gas, naphtha, and
kerosene is preferably refluxed (recycled) back to the primary tower to enhance fractionation
and efficiency. Wet gas is withdrawn from the primary tower 26 through overhead wet
gas line 28. Light naphtha is removed from the primary tower through light naphtha
line 29. Intermediate naphtha is removed from the primary tower through intermediate
naphtha line 30. Heavy naphtha is withdrawn from the primary tower 26 through heavy
naphtha line 31. Kerosene and oil for producing jet fuel and furnace oil are removed
from the primary tower through kerosene line 32. Part of the kerosene and/or heavy
naphtha can be fed to the quench line 186 (Figure 1) for use as part of the quench,
if desired. Primary virgin, atmospheric gas oil is removed from the primary tower
through primary gas oil line 33 and pumped to the fluid catalytic cracking unit (FCCU)
34 (Figure 4), sometimes via a catalytic feed hydrotreating unit.
[0030] Primary reduced crude is discharged from the bottom of the primary tower 26 (Figure
3) through the primary reduced crude line 35. The primary reduced crude in line 35
is pumped by pump 36 into a furnace 38 where it is heated, such as to a temperature
from about 520°F (271°C) to about 750°F (399°C). The heated primary reduced crude
is conveyed through a furnace discharge line 40 into the flash zone of a pipestill
vacuum tower 42 or directly to the FCU reactor.
[0031] The pipestill vacuum tower 42 (Figure 3) is preferably operated at a pressure ranging
from 35 to 50 mm of mercury. Steam can be injected into the bottom portion of the
vacuum tower through steam line 44. In the vacuum tower, wet gas or vacuum condensate
is withdrawn from the top of the tower through overhead wet gas line 46. Heavy and/or
light vacuum gas oil are removed from the middle portion of the vacuum tower through
gas oil line 48 and can be fed to a catalytic feed hydrotreating unit (CFHU) 49 (Figure
4) or to the riser reactor. Vacuum-reduced crude is removed from the bottom of the
vacuum tower 42 (Figure 3) through a vacuum-reduced crude line 50. The vacuum-reduced
crude, also referred to as resid or resid oil, typically has an initially boiling
point near about 1000°F (538°C).
[0032] Some of the resid can be pumped and fed to FCCU 34 (Figure 4) via FCCU resid line
52 or upgraded in a resid hydrotreating unit (RHU) comprising a series of ebullated,
expanded bed reactors. Light gas oil (LGO) from the RHU can also be fed to the FCCU
34 via an RHU LGO line 54. Some of the resid can be pumped to a coker unit 56 via
a coker resid line 58.
[0033] The coker unit 56 (Figure 5) comprises a coker or coke drum 62 and a combined tower
64. In the coker 62, the vacuum tower bottoms are coked at a coking temperature of
about 895°F (479°C) to about 915°F (491°C) at a pressure of about 10 psig (69 kPa)
to about 50 psig (345 kPa). Coke is withdrawn from the coker 62 a through chute, conduit,
or line 66 and transported to a coke storage area for use as solid fuel. Coker product
vapors can be withdrawn from the coker 62 through coker vapor line 68 and passed (fed)
to a combined coker tower 64. In the combined coker tower 64, the coker product vapor
can be separated into fractions of coker gas, coker naphtha, light coker gas oil,
coke still distillate (coker distillate) and heavy coker gas oil. Coker gas can be
withdrawn from the combined tower 64 through coker gas line 70. Coker naphtha can
be withdrawn from the combined tower 64 through coker naphtha line 72. Coke still
distillate (coker distillate) can be withdrawn from the combined tower 64 through
coke still distillate CSD line 73. Light coker gas oil can be withdrawn from the combined
tower 64 through light coker gas line 74 and fed to the FCCU 34 (Figure 4) or the
catalytic feed hydro-treater (CFHU) 49. Part of the coke still distillate (coker distillate),
light coker gas oil, and/or coker gas can be fed to the quench line 186 for use as
part of the quench, if desired. Heavy coker gas oil can be withdrawn from the combined
tower 64 (Figure 5) through heavy coker gas oil line 76 and hydrotreated in the catalytic
feed hydrotreater (CFHU) 49 (Figure 4) before being catalytically cracked in the catalytic
cracker 34 (FCCU).
[0034] Heavy coker gas oil from heavy coker gas oil line 76 (Figure 5) and light vacuum
gas oil and/or heaving vacuum gas oil from vacuum gas oil line 48 (Figure 3) are conveyed
to the riser reactor 100, or alternatively, to the catalytic feed hydrotreater or
catalytic feed hydrotreating unit (CFHU) 49 (Figure 4) where they are hydrotreated
with hydrogen from hydrogen feed line 78 at a pressure ranging from atmospheric pressure
to 2000 psia (13.8 MPa) preferably from 1000 psia (6.9 MPa) to 1800 psia (12.4 MPa)
at a temperature ranging from 650°F (343°C) to 750°F (399°C) in the presence of a
hydro-treating catalyst. The hydrotreated gas oil is discharged through a catalytic
feed hydrotreater discharge line 80 and fed to the catalytic cracker 34 (FCCU).The
catalytic cracking reactor 34 of Figure 1 has an upright elongated vertical riser
rector 100 with an upper portion 102 and a lower portion 104. Cracking catalyst and
feed oil are mixed in the bottom of the riser reactor 100. The catalytic cracker (riser
reactor) 100 catalytically cracks feed oil in the presence of a cracking catalyst
under catalytic cracking conditions to produce an upgraded effluent product. Stream
of catalytically cracked oil containing particulates of spent coked cracking catalyst.
[0035] A gross cut inertia separator comprising an external rough cut cyclone 106 (Figure
1) is connected to and communicates with the upper portion of the riser reactor 100
via a cyclone inlet line 105. The external rough cut cyclone 106 is positioned about
and at a similar elevation as the upper portion 102 of the riser reactor 100. The
rough cut cyclone makes a gross separation of the coked catalyst from the catalytically
cracked oil. Preferably, at least 92% to 98% of the coked catalyst in the oil is removed
by the rough cut cyclone 106. Positioned downstream of the external cyclone 106 is
an upright disengaging vessel or disengager 108.
[0036] The disengaging vessel 108 (Figure 1) disengages and separates a substantial amount
of the remaining coked catalyst from the catalytically cracked oil. The disengaging
vessel 108 operates at a temperature of 900°F (482°C) to 975°F (524°C). The disengaging
vessel 108 has an upper dilute phase portion 110 with at least one internal cyclone
112, an effluent product outlet line 113, a lower dense phase portion 114, and a stripping
section 116 providing a stripper in which volatile hydrocarbons are stripped from
the coked catalyst. The stripping section can have baffles or internals 115. Stripping
steam lines and injectors 117 can be connected to the stripper 116.
[0037] Extending from the upper portion of the external cyclone 106 (Figure 1) is a cyclone
outlet line 118 providing part of the product stream line 119. The product stream
line 118 has an upper horizontal section 118, a vertical intermediate section 120,
an intermediate horizontal section 122, and an elongated vertical section 124 providing
a product stream dipleg which extends downwardly through the upper dilute phase portion
110 of the disengaging vessel 108 to the upper section of the dense phase portion
114. The product stream dipleg 124 with an internal inertia separator providing an
outlet 126 located in and communicating with the intermediate section of the upper
dilute phase portion of the disengaging vessel 108. The product stream line 118 provides
a disengaging vessel input line which extends between, connects and communicates with
the external cyclone 106 and the upper dilute phase portion 110 of the disengaging
vessel 108.
[0038] A cyclone outlet spent catalyst line, conduit, and chute provides a catalyst dipleg
128 which extends into the lower dense phase portion 114 adjacent the stripping section
116 of the disengaging vessel 108. The catalyst dipleg 128 has an upper vertical section
130, an intermediate angle section 132, a lower angle section 134, and a vertical
dipleg end section 136 with an outlet opening 137. An aeration steam line 138 can
be connected to the upper vertical section 130. A fluidizing steam line 139 can be
connected to the lower angle section 134.
[0039] A regenerator 140 (Figure 1) comprising a regenerator vessel 142 is positioned above
the disengaging vessel 108. The regenerator 140 substantially combusts and regenerates
the spent coke catalyst in the presence of a combustion sustaining oxygen-containing
gas, such as air. An upright vertical elongated lift pipe 144 provides a spent catalyst
riser and line, which extends downwardly from the lower portion of the regeneration
vessel 142 through the middle section of the dense phase portion 114 of the disengaging
vessel 108 for transporting coked catalyst from the disengaging vessel 108 to the
overhead regenerator vessel 142. A lift air injector 146 is positioned near the bottom
of the lift pipe 144 for injecting air, lifting and transporting the spent catalyst
to the regenerator vessel 142 and facilitating combustion of the coked catalyst. she
regenerator vessel 142 can have internal cyclones 148 and 150, an upper dilute phase
steam ring 152, an overhead flue gas line 154 and a lower dense phase fuel gas ring
156 and line 158.
[0040] Regenerated catalyst is discharged through a catalyst discharge line, conduit, and
chute 160 (Figure 1) to an overhead withdrawal well and vessel 162 with an optional
air ring 164 in its lower portion to offset pressure buildup. A vertical regenerated
catalyst standpipe 166 extends downwardly from the withdrawal well 162 to a slide
valve 168. A horizontal regenerated catalyst line 170 is connected to the lower portion
104 of the riser reactor 100 to convey regenerated catalyst to the riser reactor.
A fluidization steam line 171 can be connected to the regenerated catalyst line 170
below the slide valve 168.
[0041] An aeration air line 172 can be connected to the middle portion of the regenerated
catalyst standpipe 166. An aeration steam line 176 (Figure 1) can also be connected
to the lower portion 104 of the riser reactor 100. Injector nozzles 178 (Figure 1)
can be positioned in the lower portion 104 of the riser reactor 100 to inject the
feed oil into the riser reactor. In the illustrated embodiment, a combined feed oil
line 180 is connected to the nozzles 178 and to a fresh feed oil line 33. A recycle
oil line 182 can be connected to and communicate with the combined feed oil line 180
to feed heavy catalytic cycle oil (HCCO), decanted oil (DCO) and/or slurry oil to
the riser reactor 100, of up to 40%, preferably at a rate of 5% to 10%, by volume
of the fresh feed rate in fresh feed oil line 33. The temperature of the regenerator
is decreased, the temperature reduction being in the range of from about 1°F (0.5°C)
to about 20°F (11°C), by cycle oil quenching.
[0042] A catalytic cycle oil quench injection line 184, comprising a LCCO injection line
and/or an HCCO injection line, with a vertical catalytic cycle oil injector section
186 extends downwardly, connects and communicates with the vertical section 120 of
the disengaging vessel input line 118 to inject a light cycle oil (LCCO) quench and/or
a heavy catalytic cycle oil (HCCO) quench into the hydrocarbon products after the
products have exited the external cyclone 106 downstream of the riser reactor 100
and before the products have entered the disengaging vessel 108. The quench minimizes
and inhibits substantial thermal cracking of the product stream of catalytically cracked
grossly separated oil to less valuable hydrocarbons, such as fuel gas. Cycle oil quenching
stops about 75% to 90% of thermal cracking of the product oil and concurrently enhances
the yield of naphtha to increase the production of gasoline. During quenching, the
temperature of the product stream of oil being discharged from the rough cut cyclone
106 is decreased from about 30°F (17°C) to about 200°F (111°C), preferably about 50°F
(28°C) to about 80°F (44°C), such as to a range of 900°F (482°C) to about 930°F (499°C).
[0043] Cycle oil quenching enhances the conversion of feed oil to upgraded oil and increases
gasoline octane. The injection rate of the quench by volume ranges from 2% to 20%,
preferably from 5% to 15%, of the input rate of feed oil in the riser reactor 100.
Advantageously, less coke is produced in the dilute phase portion 110 of the disengaging
vessel 108. Less C₂- fuel gas is also produced during cycle oil quenching.
[0044] Mixing and vaporization of the quench can be advantageously increased to less than
5 seconds and preferably less than 3 seconds by spraying the quench with one or more
atomized quench injectors to provide a quick contact quench and assure rapid mixing.
The quench is injected at a downward velocity of 50 to 100 ft/sec (15 to 30 m/sec.)
at a residence time of 0.1 to 5 seconds, preferably less than 0.2 seconds. Losses
of quench should be avoided.
[0045] High boiling quench media improves energy recovery. The quench can be preheated,
preferably above 212°F (100°C) to enhance heat recovery and minimize heat loss. Quench
is sprayed into the external cyclone vapor exit line 118 to rapidly cool the products
before entering the reactor vessel dilute phase.
[0046] For best results, the quench is injected as soon as the reaction is completed and
immediately after the coked catalyst particulates have been grossly separated from
the product stream of catalytically cracked oil. Lesser amounts of quench are required
after catalyst separation than before catalyst separation.
[0047] It was unexpectedly and surprisingly found that the use of cycle oil quench increases
the yield of high value naphtha and can improve coke make and selectivity.
[0048] It appears that gas oil conversion beyond the riser reactor is substantially completed
in the rough cut cyclone where catalyst is present. Excess fuel gas production has
previously been associated with long residence time in the dilute phase portion of
the disengaging vessel as a result of thermal cracking before the addition of cycle
oil quench.
[0049] Regenerated catalytic cracking catalyst can be fed to the riser reactor 100 (Figure
1) through a regenerated catalyst line 170, respectively. Fresh makeup catalyst can
be added to the regenerator 140. In the FCC riser reactor, the hydrocarbon feedstock
is vaporized upon being mixed with the hot cracking catalyst and the feedstock is
catalytically cracked to more valuable, lower molecular weight hydrocarbons. The temperatures
in the riser reactor 100 can range from about 900°F (482°C) to about 1200°F (649°C),
preferably from about 950°F (510°C) to about 1040°F (560°C), at a pressure from atmospheric
pressure to about 50 psig (345 kPa). Weight hourly space velocity in the riser reactor
can range from about 5 to about 200 WHSV. The velocity of the oil vapors in the riser
reactor can range from about 5ft/sec (1.5 m/sec) to about 100 ft/sec (30 m/sec).
[0050] Suitable cracking catalysts include, but are not limited to, those containing silica
and/or alumina, including the acidic type. The cracking catalyst may contain other
refractory metal oxides such as magnesia or zirconia. Preferred cracking catalysts
are those containing crystalline aluminosilicates, zeolites, or molecular sieves in
an amount sufficient to materially increase the cracking activity of the catalyst,
e.g., between about 1 and about 50% by weight. The crystalline aluminosilicates can
have silica-to-alumina mole ratios of at least about 2:1, such as from about 2 to
12:1, preferably about 4 to 6:1, for best results. The crystalline aluminosilicates
are usually available or made in sodium form, and this component is preferably reduced,
for instance, to less than about 4 or even less than about 1% by weight through exchange
with hydrogen ions, hydrogen-precursors such as ammonium ions, or polyvalent metal
ions. Suitable polyvalent metals include calcium, strontium, barium, and the rare
earth metals such as cerium, lanthanum, neodymium, and/or naturally-occurring mixtures
of the rare earth metals. Such crystalline materials are able to maintain their pore
structure under the high-temperature conditions of catalyst manufacture, hydrocarbon
processing, and catalyst regeneration. The crystalline aluminosilicates often have
a uniform pore structure of exceedingly small size with the cross-sectional diameter
of the pores being in a size range of about 6 to 20 angstroms (0.6 to 2 nanometres),
preferably about 10 to 15 angstroms (1 to 1.5 nanometres). Silica-alumina based cracking
catalysts having a major proportion of silica, e.g., about 60% to 90% by weight silica
and about 10% to 40% by weight alumina, are suitable for admixture with the crystalline
aluminosilicate or for use as the cracking catalyst. Other cracking catalysts and
pore sizes can be used. The cracking catalyst can also contain or comprise a carbon
monoxide (CO) burning promoter or catalyst, such as a platinum catalyst, to enhance
the combustion of carbon monoxide in the dense phase in the regenerator 140.
[0051] Spent catalyst containing deactivating deposits of coke is discharged from the disengaging
vessel 108 and lifted upward through the spent catalyst riser 144 and fed to the bottom
portion of the overhead fluidized catalyst regenerator or combustor 140. The riser
reactor and regenerator together provide the primary components of the catalytic cracking
unit. Air is injected upwardly into the bottom portion of the regenerator via the
air injector line 146 and spent catalyst riser 144. The air is injected at a pressure
and flow rate to fluidize the spent catalyst particles generally upwardly within the
regenerator. Residual carbon (coke) contained on the catalyst particles is substantially
completely combusted in the regenerator 140 leaving regenerated catalyst for use in
the reactor. The regenerated catalyst is discharged from the regenerator 140 through
regenerated catalyst line 160 and fed to the riser reactor 100 via the regenerated
catalyst line 170 and the regenerated catalyst standpipe 172. The combustion off-gases
(flue gases) are withdrawn from the top of the combustor 140 through an overhead combustion
off-gas line or flue gas line 154.
[0052] As shown in Figure 6, the effluent product stream of catalytically cracked hydrocarbons
(volatized oil) is withdrawn from the top of disengaging vessel 108 through an effluent
product line 113 and conveyed to the FCC main fractionator 190. In the FCC fractionator
190, the catalytically cracked hydrocarbons comprising oil vapors and flashed vapors
can be fractionated (separated) into light hydrocarbon gases, naphtha, light catalytic
cycle oil (LCCO), heavy catalytic cycle oil (HCCO), and decanted oil (DCO). Light
hydrocarbon gases are withdrawn from the FCC fractionator through a light gas line
192. Naphtha is withdrawn from the FCC fractionator through a naphtha line 194, LCCO
is withdrawn from the FCC fractionator through a light catalytic cycle oil line 196.
HCCO is withdrawn from the FCC fractionator through a heavy catalytic cycle oil line
198. Decanted oil is withdrawn from the bottom of the FCC fractionator through a decanted
oil line 199. Part of the LCCO and/or HCCO can be recycled to the cycle oil quench
line 184 (Figure 1) for use as the quench.
[0053] Alternatively, in the main fractionator the oil vapors and flashed vapors can be
fractionated (separated) into: (a) light hydrocarbons having a boiling temperature
less than about 430°F (221°C), (b) light catalytic cycle oil (LCCO), and (c) decanted
oil (DCO). The light hydrocarbons can be withdrawn from the main fractionator through
an overhead line and fed to a separator drum. In the separator drum, the light hydrocarbons
can be separated into (1) wet gas and (2) C₃ to 430-°F (221-°C) light hydrocarbon
material comprising propane, propylene, butane, butylene, and naphtha. The wet gas
can be withdrawn from the separator drum through a wet gas line and further processed
in a vapor recovery unit (VRU). The C₃ to 430-°F (221-°C) material can be withdrawn
from the separator drum through a discharge line and passed to the vapor recovery
unit (VRU) for further processing. LCCO can be withdrawn from the main fractionator
through an LCCO line for use as part of the quench or further refining, processing,
or marketing. Decanted oil (DCO) can be withdrawn from the main fractionator through
one or more DCO lines for further use. Slurry recycle comprising decanted oil (DCO)
can be pumped from the DCO line 199 (Figure 6) at the bottom portion of the main fractionator
190 by a pump through a slurry line 182 (Figure 1) for recycle to the riser reactor
100. The remainder of the DCO can be conveyed through for further use in the refinery.
[0054] Spent deactivated (used) coked catalyst discharged from the riser reactor 100 (Figure
1) can be stripped of volatilizable hydrocarbons in the stripper section 116 with
a stripping gas, such as with light hydrocarbon gases or steam. The stripped, coked
catalyst is passed from the stripper 116 through spent catalyst line 144 into the
regenerator 140. Air is injected through air injector line 146 to fluidize and carry
the spent coked catalyst into the regenerator 140 via the spent catalyst riser 144
at a rate of about 0.2 ft/sec (0.06 m/sec) to about 4 ft/sec (1.22 m/sec). Preferably,
excess air is injected in the regenerator 140 to completely convert the coke on the
catalyst to carbon dioxide and steam. The excess air can be from about 2.5% to about
25% greater than the stoichiometric amount of air necessary for the complete conversion
of coke to carbon dioxide and steam.
[0055] In the regenerator 140 (Figure 1), the coke on the catalyst is combusted in the presence
of air so that the catalyst contains less than about 0.1% coke by weight. The coked
catalyst is contained in the lower dense phase section of the regenerator, below an
upper dilute phase section of the regenerator. Carbon monoxide (CO) can be combusted
in both the dense phase and the dilute phase, although combustion of carbon monoxide
predominantly occurs in the dense phase with promoted burning, i.e., the use of a
CO burning promoter. The temperature in the dense phase can range from about 1050°F
(566°C) to about 1400°F (760°C). The temperature in dilute phase can range from about
1200°F (649°C) to about 1510°F (821°C). The stack gas (combustion gases) exiting the
regenerator 140 through overhead flue line 154 preferably contains less than about
0.2% CO by volume (2000 ppm). The major portion of the heat of combustion of carbon
monoxide is preferably absorbed by the catalyst and is transferred with the regenerated
catalyst through the regenerated catalyst line 170 and standpipe 166 riser reactor
100.
[0056] In a catalytic cracker (riser reactor) 100, some non-volatile carbonaceous material,
or coke, is deposited on the catalyst particles. Coke comprises highly condensed aromatic
hydrocarbons which generally contain 4-10 wt.% hydrogen. As coke builds up on the
catalyst, the activity of the catalyst for cracking and the selectivity of the catalyst
for producing gasoline blending stock diminish. The catalyst particles can recover
a major proportion of their original capabilities by removal of most of the coke from
the catalyst by a suitable regeneration process.
[0057] Catalyst regeneration is accomplished by burning the coke deposits from the catalyst
surface with an oxygen-containing gas such as air. The burning of coke deposits from
the catalyst requires a large volume of oxygen or air. Oxidation of coke may be characterized
in a simplified manner as the oxidation of carbon and may be represented by the following
chemical equations:



Reactions (a) and (b) both occur at typical catalyst regeneration conditions wherein
the catalyst temperature may range from about 1050°F (566°C) to about 1300°F (704°C)
and are exemplary of gas-solid chemical interactions when regenerating catalyst at
temperatures within this range. The effect of any increase in temperature is reflected
in an increased rate of combustion of carbon and a more complete removal of carbon,
or coke, from the catalyst particles. As the increased rate of combustion is accompanied
by an increased evolution of heat whenever sufficient oxygen is present, the gas phase
reaction (c) may occur. This latter reaction is initiated and propagated by free radicals.
Further combustion of CO to CO₂ is an attractive source of heat energy because reaction
(c) is highly exothermic.
[0058] The catalytic cracker (catalytic cracking unit) of Figure 2 is generally structurally
and functionally similar to the catalytic cracker of Figure 1, except that the light
catalytic cycle oil (LCCO) quench line 284 is at an angle of inclination ranging from
about 15 degrees to about 45 degrees, preferably about 30 degrees, relative to the
vertical to increase the trajectory of the quench and enhance more uniform blending.
The regenerator vessel 242 is also positioned laterally away from the disengaging
vessel 208. For ease of understanding, the parts, elements, and components of the
catalytic cracker of Figure 2 have been given part numbers similar to the corresponding
parts, elements, and components of the catalytic cracker of Figure 1, except increased
by 100, i.e., in the 200 series, e.g., riser reactor 200, external cyclone 206, disengaging
vessel 208, stripper 216, regenerator 240, etc. The catalytic cracking reactor preferably
comprises a riser reactor. Some catalytic cracking units can have two riser reactors,
two rough cut cyclones, two slide valves, and two standpipes operatively connected
to a single regenerator and to a single disengaging vessel.
[0059] The catalytic cracker (catalytic cracking unit) of Figures 12 and 13 is generally
structurally and functionally similar to the catalytic cracker of Figure 2, except
that four internal rough cut inertia separators 306 comprising gross (rough) cut internal
cyclones are used in lieu of external cyclones to grossly separate a substantial amount
of catalyst from the catalytically cracked oil after the product stream of catalytically
cracked oil has been discharged from the riser reactor 300 via horizontal product
line 305. Four CCO quench injector lines 384 extend into the interior dilute phase
portion (zone) 310 is the disengaging vessel (disengager) 308 to locations just above
the vapor product exit 318 of the internal gross cut separators 306 to inject and
spray a CCO quench comprising LCCO and/or HCCO into the catalytically cracked oil
after most of the coked catalyst has been removed from the oil by the internal gross
cut separators 306. The quench injector lines can be positioned at an angle of inclination
ranging from about 15 degrees downwardly to about 90 degrees (horizontal) relative
to the vertical to minimize backflow of quench.
[0060] In Figure 12, a vertical outlet spent catalyst line, conduit, and chute 328 depends
downwardly from the internal gross cut separators 306 to discharge separated spent
coked catalyst into the lower dense phase portion (zone) 314 and stripping section
(stripper) 316 of the disengaging vessel 308. The top portion of the upper dilute
phase zone 310 of the disengaging vessel 308 can have five secondary internal cyclones
312. The disengaging vessel 308 and secondary internal cyclones 312 above the rough
cut separators 306, cooperate to remove the remaining coked catalyst particles (fines)
from the effluent gases and oil vapors. For ease of understanding, the parts, elements,
and components of the catalytic cracker of Figures 12 and 13 have been given part
numbers similar to the corresponding parts, elements, and components of the catalytic
cracker of Figure 2, riser reactor 300, internal rough cut cyclone 306, stripper 316,
regenerator 340, etc.
[0061] One of the major design changes implemented on FCCU 600 unit which is similar to
the catalytic cracker of Figures 12 and 13, was the use of HCCO instead of LCCO to
quench the disengager. HCCO was selected instead of LCCO to avoid flooding, i.e. exceeding
the capacity of the LCCO section of the fractionator, and to improve overall unit
heat recovery, as well as to take advantage of the greater pumping capacity of the
HCCO circuit.
[0062] The HCCO quench nozzles are positioned to maximize quench efficiency by cooling the
reaction gases as soon as they exit the cyclone. HCCO quench can reduce the disengager
temperature by 30°F (17°C) to 200°F (111°C), preferably at least about 100°F (55°C).
[0063] The catalytic cracker (catalytic cracking unit) of Figures 14 and 15 is generally
structurally and functionally similar to the catalytic cracker of Figure 12, except
the upright center, central riser reactor 400 extends vertically upwardly into the
dilute phase portion (zone) 410 of and along the vertical axis of the disengaging
vessel (disengager) 408. Coaxially positioned about the upper end 409 of the riser
reactor 400 is an internal rough (gross) cut inertia separator 406 comprising an inverted
can. The inverted can 406 has: an open bottom end 406a for discharge (egress) of separated
coked catalyst into the dense phase portion (zone) 414 and stripper section (stripper)
416 of the disengaging vessel 408; an imperforate solid planar or flat top or ceiling
406b spaced above the upper end 409 of the riser reactor 400 and providing a striker
plate upon which the catalyst laden stream of catalytically cracked oil strikes upon
exiting the upper end 409 of the riser reactor; an upper cylindrical tubular wall
406c which extends downwardly from the top 406b; an intermediate portion providing
a hood 406d extending below the upper wall 406c; and a lower cylindrical tubular wall
406e about the open bottom 406a which extends downwardly below the hood 406d.
[0064] The hood 406d (Figures 14 and 15) comprises an outwardly flared skirt. The hood 406d
has an elongated downwardly diverging upper frustroconical wall 406f, which extends
downwardly from the upper wall 406c, and has an downwardly converging frustroconical
lower wall 406g, which extends downwardly from wall 406f. The upper frustroconical
wall 406f has a pair of diametrically opposite rectangular discharge openings or windows
406h which provide outlet ports for egress (exiting) of the effluent product stream
of catalytically cracked oil after the oil has been grossly separated from the catalyst.
[0065] When the catalyst laden stream of catalytically cracked oil exits the upper end 409
(Figures 14 and 15) of the riser reactor 400, it strikes the top 406b of the internal
gross cut separator (inverted can) 406 with sufficient momentum and force to grossly
separate a substantial amount of spent coked catalyst from the catalytically cracked
oil. The separated catalyst is discharged in part by gravity flow through the open
bottom 406a of the inverted can 406. The catalytically cracked oil after being grossly
separated from the catalyst, is discharged through the windows 406h of the inverted
can 406.
[0066] A pair of diametrically opposite horizontal quench lines or injectors 484 (Figure
14) extend horizontally into the interior dilute phase portion (zone) 410 of the disengaging
vessel 408 at locations in proximity to and in alignment with the windows 406h to
inject and spray a quench comprising LCCO and/or HCCO into the catalytically cracked
oil. The quench lines 484 can be positioned at an angle of inclination ranging from
about 15 degrees downwardly to about 90 degrees (horizontal) relative to the vertical
to minimize backflow of quench.
[0067] The disengaging vessel 408 (Figure 15) and the secondary internal cyclones 412 at
the top of the disengaging vessel, above the rough cut separator 406, cooperate to
remove the remaining coke catalyst particulates (fines) from the effluent gases and
oil vapors. For ease of understanding, the parts, elements, and components of the
catalytic cracker of Figures 14 and 15 have been given part numbers similar to the
corresponding parts, elements, and components of the catalytic cracker of Figure 12,
except in the 400 series, e.g., riser reactor 400, internal rough cut separator 406,
stripper 416, regenerator 440, etc.
[0068] The catalytic cracker (catalytic cracking unit) of Figure 16 is generally structurally
and functionally similar to the catalytic cracker of Figure 12, except that the regenerator
540 is positioned below the disengaging vessel (disengager) 508. For ease of understanding,
the parts, elements, and components of the catalytic cracker of Figure 16 have been
given part numbers similar to the corresponding parts, elements, and components of
the catalytic cracker of Figure 12, except in the 500 series, e.g., riser reactor
506, stripper 516, regenerator 540, etc.
[0069] In some circumstances, it may be desirable to use a fluid bed reactor or a fluidized
catalytic cracking reactor instead of or with a riser reactor.
EXAMPLES
[0070] The following examples serve to give specific illustration of the practice of this
invention but are not intended in any way to limit the scope of this invention.
Examples 1 and 2
Examples 3 and 4
[0072] Bench study tests were performed on kerosene to simulate catalytically cracked oil
after the coke catalyst particles have been removed. In the tests of Examples 3 and
4, the quench rate was 60 grams/hr and the oil product rate was 125 grams/hour. The
quench of Example 3 was HCCO. The quench of Example 4 was LCCO. Quench results of
HCCO and LCCO were very similar and are reported below

Examples 5 and 6
[0073] Experimental tests were conducted in another catalytic cracking unit (FCCU 500) similar
to that shown in Figure 2. The test of Example 5 provided a base case without the
use of a LCCO. Catalytic cracking in the test of Example 6 was performed with a LCCO
quench. The oil feed rate was 79 MBD. Riser reactor temperature was 1020°F (549°C).
Without LCCO quench, the reactor temperature at the top of the disengaging vessel
was 12°F (7°C) below the riser reactor. At 5.6 MBD of LCCO quench, the riser reactor
temperature decreased 53°F (30°C). LCCO quench yielded a desirable decrease in drying
gas production by about 16.7% from 1140 MSCFH to 980 MSCFH, significantly increased
gasoline production 4.4% from 39.5 MBD to 41.2 MBD, and increased volume recovery
by about 1%. LCCO quenching also decreased the production of propane, propylene, and
isobutane. The operating conditions and test results are:

Examples 7-9
[0074] Further experimental tests were conducted at catalytic cracking units with cycle
oil quenches. In Example 7, LCCO quench was injected immediately after the product
exit of the external rough cut cyclone in a catalytic cracking unit (Unit Y) similar
to that shown in Figure 1 with a temporary gerry-rig quench line. Example 8, LCCO
quench was injected immediately after the product exit of two external rough cut cyclones
in another catalytic cracking unit (FCCU 500) similar to that shown in Figure 2. In
Example 9, HCCO quench was injected immediately after the product exited four internal
rough cut cyclones in a disengager in a catalytic cracking unit similar to that shown
in Figures 12 and 13. Experimental test conditions and results are shown below and
in the charts of Figures 10 and 11.
Example 7
[0075]
- Feed Rate
- 24,700 B/D
- Riser Outlet Temp.
- 951°F (511°C)
- Quench Media
- LCCO
- Quench Rate
- 1500 B/D (6.1%)
- Vapor Res Time in Disengager
- 16 sec
- Fuel Gas Reduction
- 635 M SCFD

Example 8
[0076]
- Feed Rate
- 77,000 B/D
- Riser Outlet Temp.
- 1017°F (547°C)
- Quench Media
- LCCO
- Quench Rate
- 5500 B/D (7.1%)
- Vapor Res Time in Disengager
- 9 sec
- Fuel Gas Reduction
- 5 MM SCFD

Example 9
[0077]
- Feed Rate
- 37,000 B/D
- Riser Outlet Temp.
- 980°F (527°C)
- Quench Media
- HCO
- Quench Rate
- ~3000 B/D (8.1%)
- Vapor Res Time in Disengager
- 13 sec
- Fuel Gas Reduction
- 1.5 MM SCFD

Examples 10-18
[0078] Increased reactor temperature at or above 940°F (504°C), but especially above 1000°F
(538°C) diminishes the oxidation stability of the naphtha product and gasoline. Also,
active matrix octane catalysts (cracking catalysts containing ultrastable-Y zeolite
with or without rare earth exchanged into the zeolite, supported on a carrier matrix
which exhibits cracking activity independent of the zeolite) will produce a less stable
naphtha product and gasoline than will rare earth exchanged Y catalysts, which produce
larger volumes of lower octane naphtha. Furthermore, inclusion of residual oil in
the FCU feedstock mixture will diminish the stability of the naphtha product and gasoline.
[0079] Quenching in accordance with this invention can substantially increase the oxidation
and storage stability of the naphtha product and gasoline by reducing the temperature
in the dilute phase of the disengaging vessel as quickly as possible following the
initial gross cut separation of the mixture of oil vapor product and catalyst.
[0080] Oxidation stability tests were conducted at catalytic cracking units with and without
cycle oil quenches. In Examples 10-13, gas oil feed was catalytically cracked in a
catalytic cracking unit (Unit Y) similar to that shown in Figure 1 with a temporary
gerry-rig quench line, and LCCO quench, if indicated, was injected immediately after
the product exit of the external rough cut cyclone. In Examples 14-16, gas oil feed
was catalytically cracked in a catalytic cracking unit (FCCU 500) similar to that
shown in Figure 2, and LCCO quench, if indicated, was injected immediately after the
product exit of two rough cut cyclones. In Examples 17 and 18, gas oil feed was catalytically
cracked in a catalytic cracking unit (FCCU 600) similar to that shown in Figures 12
and 13, and HCCO quench, if indicated, was injected immediately after the product
exited two internal rough cut cyclones in the disengager (disengaging vessel). Experimental
test conditions and results are shown below:

The preceding Examples 10-18 show the beneficial effects on quench of product stability.
Examples 19-48
Examples 49-54
[0082] Quenching downstream of the rough cut cyclone also reduces the yield of diolefins.
Diolefins (molecules containing two unsaturated carbon-carbon bonds) are believed
to be the product of thermal rather than catalytic cracking reactions, and are formed
in regions of the FCCU where the temperature is high, or where the residence time
is long. By reducing the temperature in the disengaging zone, the application of quench
will reduce the yield of diolefinic molecules.
[0083] C4 diolefins (butadienes, and in particular 1,3,butadiene) are considered detrimental
in subsequent processing of FCCU butylenes in an isobutane alkylation unit; they cause
a higher than desired dilution of the acid alkylation catalyst.
[0084] C5 diolefins, including, but not limited to isoprene, 1,3-pentadiene, and cyclopentadiene
are considered similarly undesirable in an FCCU product stream. If the C5 FCCU product
is charged to an isobutane alkylation unit, the C5 diolefins contained in this C5
hydrocarbon stream can cause a high dilution of the acid alkylation catalyst.
[0085] Alternatively, FCCU product streams containing C5 and high molecular weight diolefins
may be blended into product gasolines. In gasoline, diolefins are suspected to contribute
to product instability. The high reactivity of chemical compounds containing two unsaturated
bonds will cause the diolefins to rapidly react with oxygen or other substances, forming
undesired gums.
[0086] Accordingly, a process which produces a lower diolefin yield is to be desired. Quenching
of the reactor dilute phase will lower the diolefin yield. The chemical reactions
which contribute to instability in gasoline are complex. Diolefins are believed to
participate in these reactions, but it is possible that the stability improvements
with quenching in Examples 19-48 involve additional molecular compounds other than
diolefins as well.
[0087] An example of the beneficial effect of quenching in reducing diolefin yields is given
below. C5 diolefin yields from the tests are presented. Quenching is expected to change
the yield of other diolefins in a similar fashion.
[0088] Yield tests were performed in a catalytic cracking unit (FCCU 500) similar to Figure
2. Samples of the total overhead C5-430 naphtha product were obtained from the vapor
product line leaving the disengaging vessel.
[0089] The samples in Examples 50 and 51 were taken with one riser reactor out of service.
Only one riser reactor, discharging through a single external rough cut cyclone into
the common disengaging vessel, was operating.
[0090] The samples taken in Examples 49 and 52-54 were taken with both riser reactors operating.
Gas products from both external rough cut cyclones were quenched immediately downstream
of the external rough cut cyclones with LCCO, then both quenched streams entered the
common disengaging vessel.
[0091] The rates to each riser reactor in in Examples 49, 52, and 54 were identical but
were reasonably split, roughly 50/50. For Example 53, the flow rate of quench was
2500 b/d to the A outlet, 4100 b/d to the B outlet, giving a total of 6600 b/d.
[0092] The following results were obtained:

[0093] At substantially the same cracking temperature, C5 diolefin yields were reduced approximately
35-50% by the application of LCCO quenching.
Quench Selection
[0094] In general, the quench should have a boiling point of 125°F (52°C), preferably at
least 430°F (221°C) in order to have a sufficient heat capacity to effectively cool
the catalytically cracked oil product to minimize thermal cracking of the oil product
as well as to allow heat recovery at the bottom rather than the top of the fractionator.
Desirably, the quench should have a molecular weight over 90 to limit the total volumetric
expansion of the quench and oil product upon vaporization to 100% to 120%, preferably
103% to 105% or less, of the volume of the oil products without the quench, i.e.,
the volumetric expansion of the quench should be from 0 to 20%, preferably 3% to 5%
or less of the volume of the catalytically cracked oil. Furthermore, the quench should
be inactive and inert to thermal cracking at 900°F (482°C) to 1100°F (593°C) for a
residence time of 1-30 seconds in the dilute phase zone of the disengaging vessel.
Previously cracked hydrocarbons, such as LCCO, HCCO, HCN, coker gas oil and coker
distillates, are very desirable as quenches since they are less reactive to thermal
cracking than fresh unprocessed virgin stocks, such as virgin gas oil and virgin naphtha,
and hydrotreated stocks, such as hydrotreated gas oil and hydrotreated distillates.
Moreover, the quench preferably has a boiling point under 900°F (482°C) to completely
vaporize in the dilute phase of the disengager in order provide effective cooling
of the catalytically cracked oil product and avoid coking of the walls and lines of
the refinery equipment.
[0095] It is also desirable that the quench decrease C₂ fuel gas production in order to
allow higher operating temperatures at the catalytic cracking unit.
[0096] The properties of various quenches are shown in Table A, wherein water has been included
for comparison only LCCO in this patent application also includes intermediate reflux
on tower pump arounds with a boiling range, API gravity, and molecular weight similar
to that shown for LCCO in Table A.

[0097] Quenching involves injecting a fluid, preferably a liquid, into the catalytic cracking
unit, preferably immediate downstream of the gross cut separator (cyclone), to stop
the reactions. Generally, a superior quench process:
1) Will provide maximum economic benefits by effectively reducing the loss of valuable
products to the thermal reactions that occur after catalytic cracking is substantially
completed.
2. Will have minimum adverse effects on operations.
3. Will minimally affect utility costs.
[0098] Although it is quite clear that a number of fluids could be used as quench, because
the requirements of a quenching process are complex, the selection of a quench material
and implementation of quenching are neither simple nor obvious. A fluid that is outstanding
in one aspect may be unacceptable in another.
[0099] The quench fluid cools and dilutes the FCC riser products and so reduces the yield
of thermal products. Figures 7 and 8 show, i.e., the ability of various quenches to
cool the product stream, i.e., show the relative cooling capacities of different fluids.
Quenched product temperature is plotted as a function of the amount of quench addition.
The LCCO/CAT in Figure 7 means that LCCO quench was injected into the oil product
before the catalyst was grossly separated from the oil product. The quench addition,
expressed as a percentage, is the ratio of the weight of quench fluid to the weight
of the product stream. The heat capacity of the quench fluid and its heat of vaporization
(if a liquid) influence the cooling capacity. Water, included for comparison purposes,
is very effective and reduces the temperature by 20°F (11°C) per 1 wt% addition. Hydrocarbons
are also effective and reduce the temperature by approximately 7°F (4°C) per 1 wt%
addition. Less effective is steam (4°F (2°C) per 1 wt%) because it is already vaporized.
Cooling the products before removing catalyst requires tremendous amounts of quench
fluid because the catalyst holds large quantities of heat and there is so much catalyst
present (typically 6 times the weight of oil). Although water provides good cooling,
it has drawbacks that offset this advantage.

[0100] Adding a quench fluid reduces the fuel gas by decreasing the temperature of the product
diluting the concentration of riser products. The rate of thermal degradation of the
riser products (and also the hydrocarbon quench) depends upon the temperature, the
residence time in the system, the concentration of vapor, and the inherent reactivity
(thermal crackability) of the material. Reducing the concentration of riser products
slows the rate of degradation provided that the quench fluid itself has a lower thermal
crackability than the riser product. Table B gives the relative molar concentrations
of riser product initially at 1000°F (538°C) and quench fluid for various quench fluids
of different molecular weights injected at a ratio of about 15% by weight of the product.
In Table B and the following tables the C2-fuel gas reduction is relative to the instantaneous
cooling of the hydrocarbon products from 1000°F (538°C) to 900°F (482°C) with a residence
time of about 13 seconds. The quench fluids (injected as liquids) expand to different
volumes depending on the molecular weights. The lowest molecular weights provide the
maximum expansion and, therefore, the maximum dilution of the riser product. Table
B also provides an estimate of the reduction in C2-fuel gas production based on laboratory
tests and includes the relative thermal reactivity of the quench fluids. Quench fluids
that have low molecular weights give the maximum reduction in C2-fuel gas production
since C2-fuel provided measures the extent of thermal degradation, provided that the
quench fluid itself has a low susceptibility to thermal cracking.
[0101] Stability of the quench is important. A quench material that is unstable will require
excessive replacement and will itself contribute to the C2-yield. Table B includes
the thermal stability of the various fluids. The thermal stability (crackability)
was determined from laboratory tests of various quench fluids. The values in the table
are relative to the thermal stability of heavy catalytic naphtha, which will have
properties similar to riser products. Of course, the non-hydrocarbon, water, does
not crack, so its performance establishes a target for the hydrocarbons. Hydrocarbons
with low crackability give satisfactory performance.
[0102] Mixing time is also an important factor in quenching. When the quench fluid is injected
into the hot product stream, the quench and product streams must mix as quickly as
possible in order to get the maximum rate of cooling. Inefficient mixing of the two
streams allows extra time for the thermal reactions to proceed. By using atomizing
nozzles to inject the quench fluid, very small droplets are formed that disperse and
vaporize quickly.
[0103] The effect of mixing time on the reduction in thermal products is indicated in Table
C, based on laboratory results for LCCO quench:

[0104] Vapor expansion is an important factor in selecting the proper quench. Vaporized
quench enters the product recovery system and must be compatible with the process
equipment and control. Improper selection of the quench fluid can lead to upsets in
the riser discharge flow, in the separation of catalyst from the product vapors, and
can cause interference with the efficient operation of the product fractionator. In
order to minimize these disruptions, the quench fluid should give the minimum expansion
to the vapor so that erratic and extreme pressure levels are avoided. Figure 9 shows
the ratio of the volume of the quenched product stream to the product stream alone
as a function of temperature drop upon quenching for various quench fluids. The legend
LCCO/CAT in Figure 9 means that LCCO quench was injected into the oil product before
the catalyst was grossly separated from the oil product. The gases, steam and propane,
have the largest increases because substantial quantities must be added to cool the
stream, and the low molecular weight gives large volumes of gas. Water also has a
substantial vapor expansion. A water-quenched stream will have almost 20% more volume
than the product stream alone. This magnitude of expansion can affect operations adversely
and should be avoided. On the other hand, the liquid hydrocarbons exhibit a nearly
neutral volume change. For the liquid hydrocarbons, the molecular weight is typically
high enough so that the volume of gas is much less than for water. Also, the expansion
of the hydrocarbon is offset by the contraction of the cooled product so that a nearly
constant volumetric flow rate is achieved. This criterion is in contrast to the benefit
of low molecular weight diluting the product vapor.
[0105] There are practical limits on the amount of quench that is used. The benefits diminish
as the amount of quench increases. Also, the benefits are greatest the higher the
-riser product temperature. Table D illustrates this. Each pair of conditions in the
table correspond to two levels of quench addition. At 1000°F (538°C) doubling the
amount of quench reduces the C2-yield by only 45%. At 1200°F (649°C) increasing quench
by a factor of 4 brings only a 30% improvement. Once again water has been included
for comparison purposes.

[0106] Coking is another important criteria in determining the proper quench. A high tendency
to form coke is detrimental to a quench fluid. Coke deposits can restrict process
flows that could force a shutdown. Excessive coke in the regenerator could adversely
affect the unit's heat balance and economics. On the other hand, a quench fluid that
reduces coke by interaction with catalyst in the dilute zone of the disengager vessel
improves the unit's coke selectivity and economics.
[0107] The use of quench increase utilities costs. A superior quench fluid minimizes those
costs. Costs that are associated with the following: replacement of lost quench fluid;
pumping the quench fluid; incomplete heat recovery and losses; water requirements
for cooling and as boiler feed; and treatment of dirty process water.
[0108] Some hydrocarbon quench materials can thermally degrade. C2-fuel gas is produced
by the degradation. Table E presents computer model predictions on the effects of
various quench medium properties on the gross reduction in C2-. A queneh fluid that
degrades the products shows a lower C2-fuel gas reduction.

[0109] There are not any or very little additional process water cost associated with the
use of hydrocarbon fluids as quench material. Process water would have to be obtained
if water were the quench material. The use of process water has additional cost. Water
becomes contaminated when it goes through the process and must be treated to meet
pollution control regulations.
[0110] Heat recovery is another important factor in selecting the proper quench, Substantial
quantities of heat are absorbed by the quench material. This heat must be recoverable
in a usable form if the quench process is to be practical. Generally, the higher the
temperature at which heat is available, the more easily it can be recovered. Therefore,
quench fluids that boil at higher temperatures will enable better heat recovery. In
the FCC catalytic cracking unit, the heat recovery is integrated into the product
fractionator system. Low temperature energy in the fractionator system is typically
lost to cooling water. Energy in streams below approximately 212°F (100°C) to 350°F
(177°C) is not recovered. Therefore, water would be a poor quench medium from an energy-recovery
standpoint since it condenses at 212°F (100°C) at atmospheric pressure and since most
of its energy is released when it condenses. A fluid that boils just below the target
quench temperature will provide the maximum heat recovery.
[0111] In Table F, the enthalpies of some candidate quench fluids (LCCO, HCCO, HVGO Gas
Oil, Water) are given that correspond to the temperatures in the table. The heats,
Q1, Q2, Q3, Q4, are shown which are the heats absorbable above (a) 625°F (329°C),
(b) between 625°F (329°C) and 475°F (246°C), (c) between 475°F (246°C) and 325°F (163°C),
(d) and between 325°F (163°C) and 60°F (16°C), respectively. Materials that absorb
large amounts of heat at high temperatures (e.g., high Q1) are preferred, and those
that absorb heat at low temperature (e.g., high Q4) are not preferred. For the materials
in Table F, the order of preference as a quench medium is (1) HCCO, (2) LCCO, (3)
Gas Oil, and lastly Water. The quenched product temperature and Q1 upper limit for
each quench was at 900°F (482°C). The enthalpies were determined at a pressure of
20 psig (238 kPa).

[0112] Quench Material Selection:
[0113] Some quench fluids are evaluated in Table G. Different refineries may use different
quench materials to meet specific requirements or to take advantage of special opportunities.
Among the fluids examined below, LCCO is best and HCCO is second best. Water has some
serious shortcomings. The remaining materials have certain characteristics that can
reduce their attractiveness as a quench fluid.

[0114] Among the many advantages of the novel catalytic cracking and quenching process and
system are:
1. Enhanced product values and quality.
2. Greater yield of more valuable hydrocarbons.
3. Production of more naphtha and finished gasoline.
4. Higher throughput.
5. Better throughput and oxidation stability of product naphtha.
6. Decreased thermal cracking and product degradation thereby minimizing overcracking
of gasoline into ethane and light fuel gas.
7. Lower pentadiene content in the naphtha product.
8. Less low value fuel gas production.
9. Increased octane number of naphtha and finished gasoline.
10. Economical
11. Efficient
12. Effective.
[0115] Although embodiments of the invention have been shown and described, it is to be
understood that various modifications and substitutions, as well as rearrangements
of process steps, can be made by those skilled in the art without departing from the
novel spirit and scope of the invention.
1. Ein katalytisches Krackverfahren, das folgende Schritte umfaßt:
Zufuhröl wird in einem Reaktor einer katalytischen Krackanlage in Gegenwart eines
Krack-Katalysators katalytisch gekrackt, um einen katalytisch gekrackten Abflußstrom
von veredeltem, Katalysator enthaltendem Öl herzustellen;
der Katalysator wird in einem außenliegenden Grobschnitt-Separator und in einem Abscheidebehälter
im wesentlichen vom veredelten Öl abgetrennt;
das veredelte Öl wird stromabwärts des außenliegenden Grobschnitt-Separators und stromaufwärts
des Abscheidebehälters mit einem Abschreckmittel (Quencher) abgeschreckt, das wenigstens
eine Komponente, ausgewählt aus der Gruppe bestehend aus leichtem katalytischem Rückführöl,
schwerem katalytischem Rückführöl, schwerem katalytischem Naphtha, Kerosin, Cokerdestillaten,
leichtem Cokergasöl, hydrobehandeltem Destillat, frischem, unbehandeltem Rohgasöl
und frischem, unbehandeltem Rohnaphtha beinhaltet; und
das Abschreckmittel wird in einer Menge, die von 2 bis 20 Volumenprozent pro Barrel
Zufuhröl reicht, in den Strom eingespritzt.
2. Ein katalytisches Krackverfahren gemäß Anspruch 1, wobei der Reaktor der katalytischen
Krackanlage ein Riser-Reaktor ist, und das folgende Schritte umfaßt:
Rohöl enthaltendes Erdöl wird im wesentlichen entsalzt;
das entsalzte Rohöl wird in einem Ofen erhitzt;
das erhitzte Rohöl wird zu einem Primärdestillationsturm gepumpt;
das erhitzte Rohöl wird im Primärdestillationsturm in Ströme von Naphtha, Primärgasöl
und primärem abgetopptem Rohöl aufgetrennt;
das primäre abgetoppte Rohöl wird zu einem Vakuum-Rohrverdampferturm gepumpt; das
primäre abgetoppte Rohöl wird im Vakuum-Rohrverdampferturm in Ströme von Reichgas,
schwerem Gasöl und vakuumabgetopptem Rohöl aufgetrennt, wobei Rückstandsöl erhalten
wird;
ein Zufuhröl, welches das Primärgasöl vom Primärdestillationsturm enthält, wird zu
zu einem senkrecht verlängerten Riser-Reaktor einer katalytischen Krackanlage befördert;
frischer und regenerierter, kristalliner Krack-Katalysator wird dem Riser-Reaktor
zugeführt;
das Zufuhröl wird im Riser-Reaktor in der Gegenwart des Krack-Katalysators unter katalytischen
Krackbedingungen katalytisch gekrackt, um einen veredelten, abfließenden Produktstrom
von katalytisch gekracktem Öl, das verbrauchten, verkokten Katalysator enthält, herzustellen;
eine wesentliche Menge des verbrauchten, verkokten Katalysators wird stromabwärts
des Riser-Reaktors in einem außenliegenden Rohschnitt-Separator vom Produktstrom abgetrennt,
um eine Grobtrennung des verkokten Katalysators vom Produktstrom durchzuführen;
der Produktstrom wird bald nachdem der Produktstrom den außenliegenden Separator verläßt,
eingespritzt und mit einem Rückführöl-Abschreckmittel abgeschreckt, um thermisches
Kracken des Produktstroms zu weniger wertvollen Kohlenwasserstoffen wesentlich zu
minimieren und gleichzeitig zur wesentlichen Erhöhung der Benzinproduktion die Ausbeute
an Naphtha zu steigern; wobei das Abschreckmittel ein Rückführöl, ausgewählt aus der
Gruppe bestehend aus leichtem katalytischem Rückführöl und schwerem katalytischem
Rückführöl, beinhaltet, und das Abschreckmittel in einer Menge, die von ungefähr 5
bis 15 Volumenprozent pro Barrel Zufuhröl reicht, in den Produktstrom eingespritzt
wird;
der abgeschreckte Produktstrom wird in einen oberen Leichtphasenteil eines Abscheidebehälters
befördert;
eine wesentliche Menge der verbleibenden, verbrauchten, verkokten Katalysatorfeinteile
wird in wenigstens einem innenliegenden Zyklon im Leichtphasenteil des Abscheidebehälters
vom abgeschreckten Produktstrom abgeschieden und abgetrennt;
flüchtige Kohlenwasserstoffe werden aus dem verkokten Katalysator in einer Abstrippzone
des Abscheidebehälters ausgetrieben;
der gestrippte, verkokte Katalysator wird zu einem Regenerator der katalytischen Krackanlage
überführt;
Luft wird in den Regenerator eingespritzt;
der verbrauchte Katalysator wird regeneriert, indem im Regenerator im wesentlichen
Koks auf dem verbrauchten Katalysator in der Gegenwart von Luft verbrannt wird;
der regenerierte Katalysator wird zum Riser-Reaktor rückgeführt;
das Kracköl wird in einer Fraktionierkolonne in Ströme von leichten Kohlenwasserstoffgasen,
katalytischem Naphta, katalytischem Rückführöl einschließlich leichtem katalytischem
Rückführöl und abgeschlämmtem Öl aufgetrennt; und
das leichte katalytische Rückführöl wird aus der Fraktionierkolonne zu einer zwischen
dem außenliegenden Zyklon und dem Wirbelschichtreaktor liegenden Abschreckmittel-Einspritzleitung
zur Verwendung als besagtes Abschreckmittel rückgeführt.
3. Ein katalytisches Krackverfahren, das die folgenden Schritte umfaßt:
Zufuhröl wird in einem Reaktor einer katalytischen Krackanlage in der Gegenwart eines
Krack-Katalysators katalytisch gekrackt, um einen katalytisch gekrackten Abflußstrom
von veredeltem, Katalysator enthaltendem Öl herzustellen;
der Katalysator wird vom veredelten Öl in einem innenliegenden Grobschnitt-Separator
in einem Abscheidebehälter im wesentlichen abgetrennt, wobei der innenliegende Grobschnitt-Separator
einen Trägheits-Separator umfaßt, ausgewählt aus der Gruppe bestehend aus einem innenliegenden
Zyklon und einem umgekehrten Becherseparator (inverted can separator); und
das veredelte Öl wird stromabwärts des innenliegenden Grobschnitt-Separators im Abscheidebehälter
mit einem Abschreckmittel, das wenigstens eine Komponente, ausgewählt aus der Gruppe
bestehend aus leichtem katalytischem Rückführöl, schwerem katalytischem Rückführöl,
schwerem katalytischem Naphtha, Kerosin, Cokerdestillaten, leichtem Cokergasöl, hydrobehandeltem
Destillat , frischem, unbehandeltem Rohgasöl und frischem unbehandeltem Rohnaphtha,
umfaßt, abgeschreckt, wobei das Abschreckmittel in einer Menge, die von 2 bis 20 Volumenprozent
pro Barrel Zufuhröl reicht, in den Strom eingespritzt wird.
4. Ein katalytisches Krackverfahren gemäß Anspruch 3, wobei der Reaktor in der katalytischen
Krackanlage ein Riser-Reaktor ist, und das folgende Schritte umfaßt:
Rohöl enthaltendes Erdöl wird im wesentlichen entsalzt;
das entsalzte Rohöl wird in einem Ofen erhitzt;
das erhitzte Rohöl wird zu einem Primärdestillationsturm gepumpt;
das erhitzte Rohöl wird im Primärdestillationsturm in Ströme von Naphtha, Primärgasöl
und primärem abgetopptem Rohöl aufgetrennt;
das primäre abgetoppte Rohöl wird zu einem Vakuum-Rohrverdampferturm gepumpt;
das primäre abgetoppte Rohöl wird im Vakuum-Rohrverdampferturm in Ströme von Reichgas,
schwerem Gasöl und vakuumabgetopptem Rohöl aufgetrennt, wobei Rückstandsöl erhalten
wird;
ein Zufuhröl, welches das Primärgasöl vom Primärdestillationsturm enthält, wird zu
einem senkrecht verlängerten Riser-Reaktor einer katalytischen Krackanlage befördert;
frischer und regenerierter, kristalliner Krack-Katalysator wird dem Riser-Reaktor
zugeführt;
das Zufuhröl wird im Riser-Reaktor in Gegenwart des Krack-Katalysators unter katalytischen
Krack-Bedingungen katalytisch gekrackt, um einen veredelten, abfließenden Produktstrom
von katalytisch gekracktem Öl, das verbrauchten, verkokten Katalysator enthält, herzustellen;
eine wesentliche Menge des verbrauchten, verkokten Katalysators wird in einem innenliegenden
Rohschnitt-Separator in dem Leichtphasenteil eines stromabwärts des Riser-Reaktors
gelegenen Abscheidebehälters vom Produktstrom abgetrennt, um eine Grobtrennung des
verkokten Katalysators vom Produktstrom durchzuführen;
der Produktstrom wird, bald nachdem der Produktstrom den innenliegenden Separator
verläßt, eingespritzt und mit einem Rückführöl-Abschreckmittel abgeschreckt, um thermisches
Kracken des Produktstroms zu weniger wertvollen Kohlenwasserstoffen wesentlich zu
minimieren und gleichzeitig zur wesentlichen Erhöhung der Benzinproduktion die Ausbeute
an Naphtha zu steigern, wobei das Abschreckmittel ein Rückführöl, ausgewählt aus der
Gruppe bestehend aus leichtem katalytischem Rückführöl und schwerem katalytischem
Rückführöl, beinhaltet, und das Abschreckmittel in einer Menge, die von ungefähr 5
bis 15 Volumenprozent pro Barrel Zufuhröl reicht, in den Produktstrom eingespritzt
wird;
eine wesentliche Menge der verbleibenden, verbrauchten, verkokten Katalysatorfeinteile
wird in wenigstens einem innenliegenden Zyklon im Leichtphasenteil des Abscheidebehälters
vom abgeschreckten Produktstrom abgeschieden und abgetrennt;
flüchtige Kohlenwasserstoffe werden aus dem verkokten Katalysator in einem Abstrippbereich
des Abscheidebehälters ausgetrieben; der gestrippte, verkokte Katalysator wird zu
einem Regenerator der katalytischen Krackanlage überführt;
Luft wird in den Regenerator eingespritzt;
der verbrauchte Katalysator wird regeneriert, indem im Regenerator im wesentlichen
Koks auf dem verbrauchten Katalysator in der Gegenwart von Luft verbrannt wird;
der regenerierte Katalysator wird zum Riser-Reaktor rückgeführt;
das abgeschreckte, katalytisch gekrackte Öl wird in einer Fraktionierkolonne in Ströme
von leichten Kohlenwasserstoffgasen, katalytischem Naphtha, katalytischem Rückführöl
einschließlich leichtem katalytischem Rückführöl und abgeschlämmtem Öl aufgetrennt;
und
das leichte katalytische Rückführöl wird zur Verwendung als besagtes Abschreckmittel
aus der Fraktionierkolonne zum Abscheidebehälter rückgeführt.
5. Ein katalytisches Krackverfahren gemäß Anspruch 2 oder 4, das die Zufuhr eines Teils
des Rückstandsöls zum Riser-Reaktor zur Verwendung als Teil des Zufuhröls beinhaltet,
und wobei das Abschreckmittel aus schwerem katalytischem Rückführöl besteht.
6. Ein katalytisches Krackverfahren gemäß Anspruch 2 oder 4, wobei leichtes katalytisches
Rückführöl wenigstens als Teil des Abschreckmittels in das Zufuhröl eingespritzt wird.
7. Ein katalytisches Krackverfahren gemäß Anspruch 4, wobei: die Trennung ein Aufprallen
des abfließenden Produktstroms beim Verlassen des Riser-Reaktors gegen eine Aufprallplatte
eines umgekehrten Becherseparators, den Austrag des abgetrennten Katalysators durch
den offenen Boden des umgekehrten Becherseparators, und die Überführung des abgetrennten,
katalytisch gekrackten Öls durch wenigstens ein, einen Produktauslaß des umgekehrten
Becherseparators beinhaltendes Fenster einschließt; und
das Abschrecken Zerstäuben des Rückführöls in der Nähe des Fensters des umgekehrten
Becherseparators beinhaltet.
8. Eine katalytische Krackanlage, die umfaßt:
einen senkrecht verlängerten Riser-Reaktor (100; 200) zum katalytischen Kracken von
Zufuhröl in der Gegenwart eines Krack-Katalysators, um einen veredelten, abfließenden
Produktstrom von katalytisch gekracktem Öl zu erzeugen, wobei verkokter Katalysator
zurückbleibt und der Riser-Reaktor einen oberen Teil und einen unteren Teil besitzt;
einen außenliegenden Rohschnitt-Separator (106; 206), der an den oberen Teil des Riser-Reaktors
angeschlossen ist und mit ihm in Verbindung steht, und der mit einem Zwischenraum
abgetrennt ist, daran angebracht ist und sich in einer im wesentlichen gleichen Höhe
wie der obere Teil des Riser-Reaktors befindet, um eine Grobtrennung des verkokten
Katalysators vom katalytisch gekrackten Öl durchzuführen;
einen aufrechten Abscheidebehälter (108; 208), um eine wesentliche Menge von verbleibendem
verkoktem Katalysator vom katalytisch gekrackten Öl im wesentlichen abzuscheiden und
zu trennen, wobei der Abscheidebehälter eine obere Leichtphasenzone mit wenigstens
einem innenliegenden Separator, eine untere Schwerphasenzone und einen Abstrippbereich
mit einem Stripper besitzt;
eine Produktleitung (120; 220), die sich zwischen dem außenliegenden Separator und
dem oberen Dünnphasenteil des Behälters erstreckt und diese verbindet;
eine Leitung für den verbrauchten Katalysator (128; 228), die sich zwischen dem außenliegenden
Separator und dem Schwerphasenteil des Abscheidebehälters erstreckt und diese verbindet;
einen Regenerator (140; 240), der einen Behälter (142; 242), ein senkrecht verlängertes
Steigrohr zum Transport von verkoktem Katalysator zum Regenerator, eine Lufteinspritzvorrichtung
(146; 246), die mit dem Steigrohr in Verbindung steht, um Luft einzuspritzen und die
Verbrennung des verkokten Katalysators zu erleichtern, und eine mit dem Riser-Reaktor
verbundene Leitung (166; 266) für den regenerierten Katalysator zur Beförderung des
regenerierten Katalysators zum Riser-Reaktor, und eine Einspritzleitung für das Rückführöl-Abschreckmittel
(184; 284) umfaßt, die an die Zufuhrleitung angeschlossen ist und mit ihr in Verbindung
steht, um, nachdem das katalytisch gekrackte Öl den außenliegenden Separator stromabwärts
des Riser-Reaktors verlassen hat und vom Katalysator grob abgetrennt wurde und bevor
das katalytisch gekrackte Öl den Abscheidebehälter erreicht, ein Abschreckmittel,
das Rückführöl umfaßt, ausgewählt aus der Gruppe bestehend aus leichtem katalytischem
Rückführöl und schwerem katalytischem Rückführöl, in das katalytisch gekrackte Öl
einzuspritzen, um die Ausbeute an Naphtha zu erhöhen und thermisches Kracken des Ölproduktstroms
wesentlich zu vermindern, wobei die Leitung für das Rückführöl-Abschreckmittel eine
im wesentlichen senkrechte Einspritzvorrichtung für leichtes Rückführöl beinhaltet,
um das Abschreckmittel im wesentlichen senkrecht abwärts in die Zufuhrleitung einzuspritzen,
oder sich in einem Neigungswinkel im Bereich von ungefähr 15 Grad bis ungefähr 45
Grad relativ zu einer senkrechten Bezugslinie befindet, um die Durchmischung des Abschreckmittels
mit den Produkten zu erhöhen.
9. Eine katalytische Krackanlage, die umfaßt:
einen senkrecht verlängerten Riser-Reaktor (300; 400; 500) zum katalytischen Kracken
von Zufuhröl in der Gegenwart eines Krack-Katalysators, um einen veredelten, abfließenden
Produktstrom von katalytisch gekracktem Öl zu erzeugen, wobei verkokter Katalysator
zurückbleibt und der Riser-Reaktor einen oberen Teil und einen unteren Teil besitzt;
einen senkrechten Abscheidungsbehälter (308; 408; 508), der mit dem Riser-Reaktor
in Verbindung steht, um eine wesentliche Menge von verkoktem Katalysator vom katalytisch
gekrackten Öl im wesentlichen abzuscheiden und zu trennen, wobei der Abscheidungsbehälter
eine obere Leichtphasenzone mit wenigstens einem innenliegenden Zyklon, eine untere
Schwerphasenzone und einen Abstrippbereich mit einem Stripper besitzt;
einen innenliegenden Grobschnitt-Separator (306; 406; 506), der in der Leichtphasenzone
des Abscheidungsbehälters angebracht ist, um eine Grobtrennung des verkokten Katalysators
vom katalytisch gekrackten Öl vorzunehmen, wobei der innenliegende Grobschnitt-Separator
eine mit einem Ölauslaß versehene Dampföffnung (318; 406h; 518) festlegt, und einen
unteren, mit einem Katalysatorauslaß versehenen Teil (328, 406e, 528) besitzt;
einen Regenerator (340; 440; 540), der einen Behälter (142; 242), ein senkrecht verlängertes
Steigrohr zum Transport von verkoktem Katalysator vom Abscheidungsbehälter zum Regenerator,
eine Lufteinspritzvorrichtung (146; 246), die in Verbindung mit dem Steigrohr steht,
um Luft einzuspritzen und die Verbrennung des verkokten Katalysators zu erleichtern,
und eine mit dem Riser-Reaktor verbundene Leitung für den regenerierten Katalysator,
um den regenerierten Katalysator zu dem Riser-Reaktor zu befördern, umfaßt; und
wenigstens eine Einspritzleitung für das Rückführöl-Abschreckmittel (384; 484; 584),
die sich in das Innere des Abscheidungsbehälters erstreckt und im wesentlichen zur
Erfassung auf den Ölauslaß des innenliegenden Grobschnitt-Separators ausgerichtet
ist, um, nachdem das katalytisch gekrackte Öl den Ölauslaß des innenliegenden Grobschnitt-Separators
verlassen hat und grob vom Katalysator abgetrennt wurde, ein Abschreckmittel, das
aus Rückführöl besteht, ausgewählt aus der Gruppe bestehend aus leichtem katalytischem
Rückführöl und schwerem katalytischem Rückführöl, in das katalytisch gekrackte Öl
einzuspritzen, um die Ausbeute an Naphtha wesentlich zu erhöhen und thermisches Kracken
des Ölproduktstroms wesentlich zu vermindern.
10. Eine katalytische Krackanlage gemäß Anspruch 9, wobei die Leitung für das Rückführöl-Abschreckmittel
(384; 484; 584) sich in einem Neigungswinkel im Bereich von ungefähr 15 Grad bis ungefähr
90 Grad relativ zu einer senkrechten, sich durch den Abscheider erstreckenden Bezugslinie
befindet, um einen Rückfluß des Abschreckmittels wesentlich zu minimieren.
11. Eine katalytische Krackanlage gemäß Anspruch 9, wobei der Regenerator (540) unter
dem Abscheidungsbehälter (508) angebracht ist und die katalytische Krackanlage eine
im wesentlichen waagrechte Röhre (505) beinhaltet, die sich zwischen dem Kopfteil
des Riser-Reaktors (500) und dem innenliegenden Grobschnitt-Zyklon (506) erstreckt
und diese verbindet.