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RFCC units set new standard for

propylene production
RFCC units are being commissioned and operated to convert hydrotreated and
straight-run resid to high levels of propylene

Patrick Walker and Raymond Peterman UOP LLC, a Honeywell Company

W
orldwide demand for propylene contin- Relative to VGO, resid contains larger quantities
ues to rise at a rapid pace. of polycyclic aromatics and smaller quantities of
Consequently, propylene continues to paraffins. Relative to VGO, resid has a lower API
command a substantial price premium over most gravity and lower hydrogen content. Conradson
other refined products. Refiners have long carbon and heterocyclics of sulphur, nitrogen
exploited this price structure by designing and and oxygen, as well as organometallics of nickel
operating their conventional fluid catalytic crack- and vanadium tend to concentrate in the heavi-
ing (FCC) units to produce higher levels of est fraction. See Figure 1 for a description of
propylene. In recent years, refiners have these phenomena.1
extended this practice to converting residual Aromatic rings cannot be opened in an FCC
feedstocks to propylene. This article explores the unit due to the low hydrogen partial pressure.
technical challenges and opportunities presented Consequently, the potential conversion of resid
when targeting high propylene
production from a residual fluid
catalytic cracking (RFCC) unit. Kero, jet, diesel, No.2 FO Vacuum gas oil Vacuum resid.
The discussion will focus on the Gas C1-C4 Naphtha/gasoline Light gas oil Heavy gas oil Lube fraction
operation of propylene-targeted Boiling points, F
grassroots RFCC units designed 100 200 300 400 500 600 700 800 900 1000
by UOP and commissioned in 100 Tri
Dinu nu
Mon clea cle Residue
the past few years. The discus- o nucle
ar ar
r arom
atic
ar
aro
oma s ma
sion will also include a summary 80
t ic s t i cs
Composition, vol%

of advances in RFCC operations Tri


cy
clo
and reliability. Mo
n pa
r
60 oc aff
Asphaltenes

ycl ins
op Di
Resins

ara cy
clo
Unique features of resid FCC ffin
s pa
ra
ffin
operations 40 iso-
par s
affi
Resid FCC operations differ ns

from conventional VGO FCC 20


operations in several important n-paraffins
Waxes
ways: feed characteristics, oper- Heterocyclic
ating conditions, catalyst and 0
5 6 7 8 9 10 11 12 13 14 15 16 17 18 20 22 24 26 28 32 36 60+
equipment design. Approximate carbon number

RFCC feed characteristics


Resid is the heaviest fraction in Figure 1 Relative quantities and boiling range of the major hydrocarbon
the barrel of crude oil boiling at classes in crude from the Ponca City Field, Ponca City, Oklahoma
the highest temperatures. Source: Marcel Dekker 1

www.digitalrefining.com/article/1000656 PTQ Q4 2012 1


feedstocks to smaller, more valuable molecules is of the regenerator internal equipment while
limited. Often, about 75% of the Conradson increasing operating costs due to accelerated
carbon in the feedstock will wind up as addi- catalyst deactivation.
tional coke,2 which is subsequently burned in the Therefore, when presented with heavily
regenerator, releasing large quantities of heat. contaminated feedstock, operating conditions
must be adjusted to cool down the regenerator.
RFCC operating conditions One way to do this is to operate the regenerator
When processing heavily contaminated feed- in partial combustion, with a flue gas CO2/CO
stock in an RFCC unit, contaminant coke will mole ratio of about 2 to 6. This is effective
deposit on the catalyst as it passes through the because burning coke partially to CO releases
reactor. Contaminant coke is unique to RFCC about one-third as much heat as burning coke all
unit operations and is formed in two ways: the way to CO2. However, this technique alone is
Conradson carbon in the feedstock will prefer- insufficient for heavily contaminated feedstock
entially wind up as coke; metals in the and would likely result in a severe operating cost
feedstock, which accumulate on the catalyst penalty due to high catalyst consumption rates.
particles, catalyse the formation of coke. For heavily contaminated feedstock, direct
Collectively, these two types of contaminant removal of heat from the catalyst in the regener-
coke contribute very little to conversion. ator via a catalyst cooler is required in addition
Additional coke (catalytic coke) must be to operating in partial combustion.
produced in sufficient quantity to ensure an Decreasing the CO2/CO ratio or increasing the
acceptable level of conversion. A third type of catalyst cooler duty have a similar impact on the
coke (catalyst circulation coke) can also be operation of the unit. Both measures result in a
carried into the regenerator due to imperfect reduction in the regenerator temperature,
stripping.3 Catalyst circulation coke is not increasing the catalyst-to-oil ratio, and thereby
tightly adhered to the catalyst particle but increasing the conversion of feed to gasoline and
rather constitutes heavy hydrocarbon remaining lighter products. The coke is ultimately burned
in the emulsion phase.4 Thus, efficient stripping in the regenerator and recovered as superheated
is critical for resid operations. The total coke high-pressure steam via the catalyst cooler and
yield (lb coke/lb feed) is controlled by the oper- the heat recovery section downstream of the CO
ating conditions of the plant. For a clean incinerator. This way, incremental contaminant
feedstock, reasonable conversion might be coke is rejected from the feedstock and burned
achieved with a coke yield of around 5 wt% on to produce high-quality steam suitable for driv-
feed. For a resid feedstock, the coke yield might ing large turbines such as the main air blower or
be greater than 10 wt% on feed in order to the wet gas compressor.
reject the contaminant coke while maintaining
catalytic coke at a quantity sufficient for reason- RFCC catalyst
able conversion. Cracking catalyst for resid feedstock should have
The weight fraction of coke (of all types several features beyond those characteristics of
combined) that deposits on the catalyst during a cracking catalyst for VGO feedstock. More specif-
single pass through the reactor is known as ically, the catalyst structure must be designed to
coke (lb coke/lb catalyst). coke is a function of accommodate the large polycyclic aromatic
the feed properties, catalyst properties, operating molecules associated with resid feedstocks. This
conditions and reactor technology. For heavily is usually accomplished by the incorporation of
contaminated feedstock, delta coke can be matrix components that contain a significant
greater than 1.0 wt%. pore volume. The catalyst also needs a low
The regenerator temperature is a strong func- coke character to counter the high coke
tion of coke. At constant operating conditions, tendencies of the contaminated feedstock.
higher coke resulting from elevated contami- Finally, the catalyst needs to be tolerant of the
nants in the feedstock and higher metals on the metals in the feed, notably nickel and vanadium.
catalyst leads to a higher regenerator tempera- Modern cracking catalyst deactivates rapidly at
ture. Operations at higher regenerator temperatures above around 1350-1375F (730-
temperatures can reduce the useful working life 745C). This is due to hydrothermal deactivation,

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caused by high temperatures and a steam concentrate in the heaviest fraction of the feed-
environment, whereby the zeolite structure liter- stock. Nickel is a dehydrogenation agent and
ally collapses. Most refiners have discovered that catalyses the formation of H2 and coke.
the operating costs associated with high catalyst However, nickel deposits on the surface of the
consumption become prohibitive at regenerator catalyst particle and, once deposited, tends to
temperatures above 1375-1400F (745-760C). be stationary. The signature symptom of nickel
Thus, there is a need for a catalyst exhibiting low poisoning is high H2 formation, which results in
coke characteristics, which is accomplished high dry gas production. This can be countered
through specific catalyst design features as well by modern nickel trapping technology, lift gas
as targeting an equilibrium catalyst activity that and antimony to passivate the dehydrogenation
is lower than that associated with VGO catalyst. impact of the nickel. New nickel will deposit on
Cracking catalyst also deactivates via the top of old nickel, rendering old nickel inactive.
sodium and vanadium that accumulates on the As a consequence, H2 production tends to rise
catalyst. Sodium neutralises some of the acid rapidly with the initial nickel deposits, but then
sites within the zeolite structure, rendering those tapers off with further increases in nickel.
acid sites permanently inactive. Vanadium Incremental nickel levels much above 8000
deposited on the catalyst particle surface oxidises wppm produce very little incremental H2.5
in the regenerator to V2O5, which in the presence
of steam becomes mobile Resid FCC equipment
vanadic acid (H3V04) that Heavily contaminated resid is
migrates throughout the cata- often processed in an RFCC unit
lyst particle and then destroys employing a two-stage regenera-
the zeolite silica-alumina tor with catalyst coolers. This
framework. technology was first commercial-
Sodium poisoning is usually ised in 1983 at the Ashland Oil
caused by sodium chloride Refinery located in Catlettsburg,
that enters the crude unit Kentucky.6,7
during a desalter upset. This is
well controlled in most refin- Processing resid with a two-stage
eries by using double desalters regenerator
in the crude unit. Fresh cata- Referring to Figure 2, fully regen-
lyst typically has 2000 to 3000 erated catalyst exiting the
wppm sodium left over from second-stage regenerator is trans-
the manufacturing process. ferred through the regenerated
Additive sodium beyond 5000 catalyst standpipe to the wye.
wppm on equilibrium catalyst From the wye, the catalyst is lifted
can cause a rapid decline in with a mixture of steam and
catalyst activity. sponge gas part way up the riser
Vanadium is organically to the UOP Optimix feed distribu-
bound within organometallic tors. Cracking now commences
molecules and tends to and continues as the catalyst is
concentrate in the heaviest lifted further to the UOP VSS riser
fraction of the feedstock. With termination device followed by a
modern vanadium trapping single stage of cyclones. Spent
technology, concentrations of catalyst then proceeds down the
up to 7000 wppm vanadium stripper containing UOP AF strip-
on equilibrium catalyst can be ping technology. The spent
tolerated while maintaining catalyst is transferred through the
suitable catalyst activity. spent catalyst standpipe into the
Nickel is also organically first stage of the regenerator,
bound within organometallic Figure 2 UOP RFCC unit two-stage where the catalyst is partially
molecules and tends to regenerator with catalyst cooler regenerated. The partially

www.digitalrefining.com/article/1000656 PTQ Q4 2012 3


returned to the reactor is fully regener-
ated and the active catalyst sites are
restored to the maximum extent
possible.

Processing resid with a combustor regenerator


Several refiners process resid in FCC
units employing a UOP Combustor
Regenerator. This type of regenerator
operates in full combustion, so the cata-
lyst is fully regenerated in a single stage.
Operating in full combustion eliminates
the need for a CO incinerator because
the flue gas exiting the regenerator has
minimal carbon monoxide.
Spent catalyst exiting the reactor strip-
per is transferred through the spent
catalyst standpipe into the combustor
(lower vessel) where the catalyst is fully
regenerated. During regeneration, the
catalyst is lifted by the main air up into
the regenerator (upper vessel) where it is
collected and distributed (see Figure 3).
Some of the collected catalyst is
returned to the combustor through the
catalyst cooler and cooled catalyst stand-
pipe. Additional catalyst is returned to
Figure 3 UOP Combustor Regenerator the combustor through the recirculation
catalyst standpipe, which increases the
regenerated catalyst is then transferred into the combustor temperature and accelerates the
second stage of the regenerator via flow-through combustion kinetics. The remaining catalyst is
catalyst cooler(s), with the excess catalyst trans- returned to the reactor via the regenerated cata-
ferred through the circulation catalyst standpipe. lyst standpipe.
In the second stage, regeneration of the catalyst Reactor side equipment is similar to that previ-
is completed and catalyst is returned to the wye. ously described for a two-stage regenerator.
Combustion air is delivered to both stages. Flue Feedstocks containing as much as 2-3 wt%
gas exiting the second stage is transferred up Conradson carbon can be reasonably processed in
into the first stage, where it co-mingles with a combustor regenerator without a catalyst cooler.
incoming fresh air. The combined flue gas exits For Conradson carbon levels exceeding 2-3 wt%,
the first-stage regenerator to a CO incinerator the regenerator temperature becomes excessive,
followed by a waste heat recovery section, which and a catalyst cooler is required to manage cata-
produces high-pressure superheated steam. lyst deactivation and maintain reasonable
The first-stage regenerator operates in partial conversion.
combustion with a CO2/CO mol ratio of about Processing feedstock containing greater than 4
3.0. Since the combined net flue gas departs wt% Conradson carbon was once considered the
from the first stage, the regenerator overall oper- exclusive domain of two-stage regenerators.
ates in partial combustion, thereby cooling off However, in recent years, several refiners have
the regenerator. However, the catalyst exiting processed increasingly contaminated residual
the first stage is only partially regenerated and feedstock (up to 6 wt% Conradson carbon) in
the activity is suppressed by the remaining coke. combustor regenerators with catalyst coolers.
The second stage operates in complete combus- A major advantage of a combustor regenerator
tion with excess oxygen. This ensures the catalyst is the ability to produce the lowest combined

4 PTQ Q4 2012 www.digitalrefining.com/article/1000656


levels of CO and NOx compared Catalyst cooler duty ranked by shell diameter
to all other available regenerator
technologies. It is not unusual
for emissions from a combustor Shell diameter, ft. 6 7 8 9
regenerator to be less than 50 Relative duty, % 100 150 200 250
wppm for both pollutants.
Table 1
Catalyst coolers drive
conversion
Catalyst coolers provide the flex-
ibility to maintain conversion Operating unit

when feed quality deteriorates. Single-stage


This might happen when taking
down a feed hydrotreater for
catalyst replacement or when Single-stage with
catalyst cooler
processing more contaminated
crudes.
Structural and mechanical Two-stage with
design of the plant typically catalyst cooler
limits the number of catalyst 0 2 4 6 8 10
coolers that can be reasonably Feed Conradson Carbon, wt%
arranged around the regenera-
tor. Early-generation catalyst Figure 4 UOP RFCC experience, grouped by type of regenerator; single stage
coolers were limited in size to = combustor regenerator or bubbling bed regenerator
6ft or 7ft diameter. In recent
years, several 8ft-diameter
catalyst coolers as well as two 40
9ft-diameter catalyst coolers Two stage regenerator with catalyst cooler
have been commissioned. In Combustor regenerator with catalyst cooler
Feed Ni+V, wt ppm

addition to larger diameters, 30


tube lengths have increased.
Both measures increase the
heat transfer surface area and, 20
hence, the capacity of a catalyst
cooler.
10
Table 1 shows the relative duty
of each size catalyst cooler. With
larger catalyst coolers it is easier 0
to arrange a larger amount of 3 4 5 6 7 8 9
cooling capacity around the Feed ConCarbon, wt%
regenerator. This expands the
working range of combustor Figure 5 UOP RFCC units processing heavily contaminated feedstock
regenerators into territory once
reserved for two-stage regenerators. An 8ft- grouped by type of regenerator. Figure 5
diameter catalyst cooler is capable of removing describes in greater detail the subset of the most
the heat equivalent of about 1.5 wt% Conradson contaminated feedstocks processed in units
carbon from an having one or more catalyst coolers.
80 000 b/d RFCC unit.
In general terms, RFCC refers to FCC units How propylene is produced in a catalytic
processing feedstock containing 2.0 wt% cracking unit
Conradson carbon or greater. Based on this defi- Where propylene is produced
nition, Figure 4 shows UOPs RFCC experience, Propylene is produced primarily in the riser

www.digitalrefining.com/article/1000656 PTQ Q4 2012 5


section of the FCC unit through a complex
combination of thermal and catalytic reactions
(see Figure 6).

Operating variables that impact propylene production


The principal operating variables that impact
propylene production are reactor temperature,
ZSM-5 concentration, hydrocarbon partial pres-
sure and feed properties. Table 2 describes how
each of these properties impacts propylene
production. Equipment design can also have a
profound impact on propylene production.8
High hydrocarbon partial pressure tends to
shift the equilibrium of cracked products from
olefins to paraffins. Hence, higher propylene
production is achieved at lower riser absolute
pressure and higher riser steam concentration.
Vanadium has a negative impact on ZSM-5
activity. UOP has observed this impact both in
commercial plants and through laboratory test-
Most of the
ing. ZSM-5 appears to be less efficient in units
propylene is
produced by processing feedstocks with high levels of
catalytic and vanadium.
thermal cracking in
the riser
Feed properties
Propylene production is highly dependent on
feed properties. Typical RFCC feedstocks are
highly aromatic (low UOP K) and consequently
resistant to conversion at typical riser residence
times. Typical RFCC feedstocks also have a low
hydrogen content, frequently 12.0 to 12.5 wt%
hydrogen, while propylene requires a dispropor-
tionate share of the hydrogen at 14.3 wt%.
Like dry gas, some Co-products including propane and dry gas
of the propylene require an even greater share of hydrogen.
is produced by Hence, the amount of hydrogen available from
thermal cracking in
the feedstock can limit the potential to produce
the hottest part of
the riser just above propylene.
the feed distributors Conradson carbon is another important factor.
Much of the Conradson carbon winds up as coke,
thereby reducing the potential pool of liquid and
gas products, including propylene.

Impact of hydrotreating
Table 3 shows a comparison of the feed proper-
ties and corresponding catalyst properties
operating in two RFCC units. One of the units
processes hydrotreated resid feedstock, while the
other processes straight-run resid feedstock.
Note the high 50% boiling point temperature
Figure 6 Propylene production in a catalytic cracking and corresponding high concentration of hetero-
unit cyclics and organometallics consistent with

6 PTQ Q4 2012 www.digitalrefining.com/article/1000656


Figure 1. Note also that the Relative impact of operating conditions on propylene production
heterocyclics and organometal-
lics are substantially lower for
Operating variable Propylene yield
the hydrotreated feedstocks. Increased reactor temperature
As mentioned previously, Increased ZSM-5 concentration
nickel is a dehydrogenation agent Increased hydrocarbon partial pressure
that increases the molecular H2 Improved feed properties
production and delta coke (which
manifests as a higher regenerator Table 2
temperature). The impact of
nickel at levels listed in Table 3,
Impact of hydrotreating on feed quality and catalyst properties
and even higher, can generally be
accommodated.
Feed type Hydrotreated resid Straight-run resid
As a catalyst poison, the maxi- Feed quality
mum achievable vanadium Base gravity, API 21.3 17.5
concentration is self-limiting at ASTM 50% boiling point, F 961 990
constant catalyst activity. If the Conradson carbon, wt% 4.2 8.5
Sulphur, wt% 0.41 2.20
catalyst addition rate is Total nitrogen, wppm 1200 2000
decreased, the vanadium concen- Nickel, wppm 4.2 20.0
tration increases and catalyst Vanadium, wppm 6.9 17.0
activity declines, forcing a higher
Catalyst properties
addition rate to maintain the Nickel, wppm 2500 7600
activity, which then reduces the Vanadium, wppm 4500 6500
concentration of vanadium. Conversion*, LV% 84.2 83.0
Propylene yield, wt% 10.7 8.2
Resid to propylene *Gasoline ASTM 90% @ 380 F
For the purposes of this discus-
sion, primary conversion
means traditional conversion of Table 3
feedstock to gasoline and
lighter, while secondary conversion means was more than three times the increment at high
conversion of gasoline boiling- range olefins primary conversion.
(produced during primary conversion) to LPG ZSM-5 appeared to be less effective at higher
olefins. Propylene is produced by both types of primary conversion. This phenomenon could be
conversion. ZSM-5 promotes only secondary the result of the lower supply of gasoline olefins
conversion. With multiple handles available for available for secondary conversion via ZSM-5.
increasing propylene production, and a unique Light olefin equilibrium may also contribute to
set of trade-offs associated with each handle, the diminishing response.8
optimisation testing is required to determine ZSM-5 zeolite deactivates in the unit and is
the most profitable operating point. flushed out by equilibrium catalyst withdrawals
and therefore must be added continuously. The
Case study higher the ZSM-5 addition rate, the higher the
UOP has closely monitored optimisation testing secondary conversion, but with diminishing
at several RFCC units. In one such unit process- returns. When the ZSM-5 addition rate was
ing heavily contaminated resid, comprehensive subsequently decreased for both primary conver-
testing was done at two levels of primary conver- sion levels, the propylene yield decreased
sion at high and low ZSM-5 addition rates. substantially while the butylenes yield changed
Primary conversion was adjusted by changing the very little, suggesting that propylene selectivity is
reactor temperature. Propylene production more sensitive to ZSM-5 deactivation than buty-
increased with both primary conversion and the lenes selectivity.
ZSM-5 addition rate. At low primary conversion, The addition rate for the high ZSM-5 cases was
the incremental propylene attributable to ZSM-5 5 to 6 t/d, which is a significant operating

www.digitalrefining.com/article/1000656 PTQ Q4 2012 7


Exchanger fouling can limit heat
40 removal from the main column,
Two stage regenerator with catalyst cooler
thereby increasing tray traffic
Combustor regenerator with catalyst cooler
and overhead condenser duty
Feed Ni+V, wt ppm
30 Straight run resid.
beyond capacity. As the cold
3
27lb C H per barrel feed
6

Hydrotreated resid. Straight run resid. side of the circulating slurry is


33lb C H per barrel feed
3 6
30lb C H per barrel feed
3 6 used to heat feed, exchanger
20
fouling can also limit the feed
temperature to a sub-optimal
range. Fouling can also force a
10
frequent reduction in feed rate
Hydrotreated resid. while cleaning the exchangers.
35lb C H per barrel feed
0
3 6
The composition of slurry
3 4 5 6 7 8 9 exchanger foulant has been
Feed ConCarbon, wt% inspected on a number of plants
and frequently described as a
Figure 7 propylene production is a strong function of feedstock quality thin homogeneous layer of solid
hydrocarbon. Laboratory analysis
expense. The major driver for this high ZSM-5 has confirmed the composition to be hydrocar-
addition rate was the high cracking catalyst addi- bon, free of catalyst fines. This type of fouling is
tion (and withdrawal) rate required to maintain due to the condensation of polynuclear aromatics,
catalyst activity given the high concentration of and is a function of the residence time, tempera-
vanadium in the feedstock, whereby ZSM-5 is ture and composition of the circulating inventory.
flushed out of the unit. A useful observation regarding this type of fouling
As with most FCC units, various unit is that the slurry viscosity will increase rapidly at
constraints were lifted at lower reactor tempera- incipient fouling, so fouling can be predicted and
ture and conversion. This allowed for higher mitigated by monitoring the slurry viscosity.
throughput, which resulted in a higher gross Fouling is also a function of the tube side
margin compared with lower throughput at velocity. Since slurry oil contains abrasive cata-
higher conversion. lyst fines, a higher velocity will scrub away
The overall optimum operating condition foulant as it is produced. Indeed, high velocity
appeared to be a higher feed rate with a lower can cause tube internal erosion, so UOP specifies
reactor temperature and with higher ZSM-5 both lower and upper limits for tube side
addition. However, given a changing market velocity.
price differential between gasoline and propyl- The circulating slurry system is similar to a
ene, the optimum operating point will shift, so continuous stirred tank reactor. In this case, the
re-optimisation is required from time to time. reactants are polynuclear aromatics, which
Figure 7 provides a broader summary of the condense to form the foulant. Production
typical propylene yield from various RFCC units increases with residence time. Decreasing the
when operating in propylene mode. Note the bottoms level or increasing the net slurry produc-
consistent correlation between propylene produc- tion reduces the residence time and therefore
tion and feedstock quality. condensation reactions.
Note that several of these units comfortably At bubble point, the composition and tempera-
produce 10-11 wt% propylene. Even higher levels ture in the circulating pool track together and
are readily achievable, depending on market are directly controlled by the LCO draw rate.
economics. Fouling can be substantially controlled by reduc-
ing the LCO draw rate, but this presents a
Advances in unit operations and reliability penalty as LCO is downgraded to slurry.
Main column bottoms system fouling Quenching (sub-cooling) the slurry pool with
Circulating slurry and net slurry exchangers are cooled slurry is an effective way to break the
more likely to suffer from fouling on the tube composition-temperature relationship. Therefore,
side of the exchangers when processing resid. additional LCO can be drawn and the slurry

8 PTQ Q4 2012 www.digitalrefining.com/article/1000656


composition will become heav-
ier, but without increasing the 8000 0.40

Nickel / 10*antimony, wt ppm


pool temperature, partially miti- 7000 0.35
gating fouling. 6000 0.30

Hydrogen yield,
wt% fresh feed
Early generations of quench
5000 0.25
systems consisted of a single
nozzle with no internals, which 4000 0.20

cooled off that portion of the 3000 0.15


pool nearest the nozzle but less 2000 Nickel 0.10
so far away from the nozzle, so 10*Antimony
1000 0.05
localised high temperatures Hydrogen yield
persisted, contributing to 0 0

08

08

08

08

8
fouling.

/0

/0

/0

/0

/0

/0

/0
3/

3/

3/

3/

/3

/3

/3

/3

/3

/3

/3
6/

7/

8/

9/

10

11

12

13

14

15

16
Exchanger fouling can be
effectively mitigated by using Figure 8 Impact of antimony on H2 production
proper equipment design and
procedures, and by implementing a rigorous occur during restart. This scenario has occurred
monitoring program. A key equipment design throughout the industry since refiners first began
element is a quench distributor, which evenly processing resid. Consequently, UOP now recom-
distributes cool slurry throughout the fractiona- mends installing coke anchors (similar to
tor bottoms pool, thereby minimising localised refractory anchors) around the gas tube for
hot spots. The quench rate is adjusted to main- RFCC units. The coke anchors serve to capture
tain the target pool temperature. The normal coke deposits that might otherwise dislodge
operating liquid level is maintained on the low during a thermal cycle. Coke anchors have been
side to minimise the residence time in the pool. practised occasionally since 19999 and are gain-
Also, the circulating slurry flow rate is set to ing wider acceptance as a way to mitigate this
maximum at all times. This results in a high tube problem.
side velocity and maximises the amount of In addition to coke anchors, UOP recommends
cooled slurry available for quench. Also, a rigor- 45-degree flapper valves for the reactor cyclone
ous monitoring program is required whereby the diplegs in RFCC units. In the event a piece of
slurry viscosity, tube side velocity and exchanger coke dislodges from a gas tube, a 45-degree flap-
overall heat transfer coefficient are tracked as a per valve has an advantage because the dipleg is
function of the LCO draw rate. With these design completely free draining when the flapper valve
and procedure features, the time between clean- is wide open.
ing can be extended substantially.
Dry gas production
Reactor dipleg coke fouling Given the high nickel levels associated with
Coke deposits inside the reactor and associated processing resid, dry gas production, and specifi-
equipment are more common in resid FCC units cally molecular H2 production, can be quite
due to the coke precursors in the feedstock. Coke substantial. This is problematic because H2
deposits are most commonly found in stagnant cannot be economically recovered from dry gas
or cooled regions where precursors might plate and is thus valued as fuel gas, thereby down-
out on a surface. Perhaps the most problematic grading its value. Since H2 has a low molecular
coke deposits attach to the interior of the cyclone weight, small quantities (on a wt% basis) can
near the stagnant region on the back side of the substantially increase the flow rate of dry gas,
gas tubes. Coke deposits at this location can be which might hydraulically bottleneck the wet gas
on the same scale as the dipleg diameter. These compressor and downstream gas plant.
deposits can be dislodged as the gas tube Furthermore, since resid feedstocks are generally
contracts and expands during a thermal cycle hydrogen-deficient (less than 12.5 wt% hydro-
caused by an emergency shutdown and restart. gen), diverting just 0.1 wt% to molecular H2
If the deposits then fall into the dipleg, blocking diminishes the ability to produce propylene.
catalyst flow, high reactor side catalyst losses can Previously discussed well-proven methods for

www.digitalrefining.com/article/1000656 PTQ Q4 2012 9


UOP Combustor Regenerators
with catalyst coolers is gaining
1-ton bag loading
(old system)
wider acceptance alongside two-
stage regenerators with catalyst
Fresh cat. Purchased coolers. Catalyst coolers expand
hopper e-cat.
ZSM-5
the flexibility of these units to
hopper
hopper New tilting truck
process heavily contaminated
loaders (2) resid feedstocks, enabling high
conversion levels and high
propylene production rates.
The optimum operating condi-
tions for maximising an RFCC
Load cell Load cell
No. 1 No. 2 units profitability is a function of
many variables. In one case
study, the optimum was found to
To regenerator be at maximum throughput with
a slightly reduced conversion and
a high concentration of ZSM-5
Figure 9 Improved catalyst handling facilities additive.
Numerous other advances in
controlling nickel-catalysed molecular H2 conventional RFCC processing
production include using an antimony additive. technology have occurred in the past few years.
Figure 9 shows a dramatic drop in H2 yield when These include measures to control main column
antimony is first introduced into a unit with high bottoms system fouling, reactor cyclone dipleg
nickel concentration on the circulating catalyst. fouling and dry gas production, as well as
advanced catalyst handling facilities.
Catalyst handling
A widely practised technique for purging metals Optimix, VSS and AF are trademarks of UOP.
out of the unit is to flush with low-metals
purchased equilibrium catalyst. This reduces the
harmful effects of the metals and reduces fresh
catalyst costs. For this purpose, UOP specifies References
purchased E-Cat hoppers for RFCC units (see 1 Venuto P B, Habib E T, Jr, Fluid Catalytic Cracking with Zeolite
Figure 9). In some units, the hoppers were origi- Catalysts, Marcel Dekker Inc, New York, 1979.
nally charged from one-ton supersacks. This 2 Stokes G M, Mott R W, FCC resid processing an overview,
AIChE 1988 Annual Meeting, 2 Dec 1998.
became a bottleneck because it took a long time
3 Upson L L, The basic heat balance, 4th Annual Katalistiks FCC
to transfer catalyst from the supersacks to the
Symposium, 18-19 May 1983, Amsterdam.
hoppers. Tilting truck charging facilities were 4 Rosser F S, Schnaith M W, Walker P D, Integrated view to
subsequently added for charging the hoppers understanding the FCC NO puzzle, 2004 AIChE Spring Meeting.
x
from shipping containers. Load cell-based dosing 5 Schnaith, et al, Resid cracker handles record nickel levels,
systems were also added to accurately record the Proceedings Second Int. Pet. Conf. & Exbn. Petrotech-97, New
amount of catalyst and additive transferred into Dehli, 503-512.
the unit. 6 Hemler C L, Lomas D A, Tajbl D G, Residual catalytic cracking:
theory and practice, API 49th Midyear Meeting, 14-17 May 1984.
Summary 7 Cabrera C A, Hemler C L, FCC heat balance control effect on
resid processing efficiency and flexibility, AM-86-60, NPRA Annual
In the past few years, several RFCC units have
Meeting, 23-25 March 1986, Los Angeles, CA.
been commissioned and operated to convert
8 Knight J, Mehlberg R, Creating opportunities from challenges:
resid to high levels of propylene utilising UOPs
maximizing propylene yields from your FCC, AM-11-06, NPRA
resid FCC process technology. Included among Annual Meeting, 20-22 March 2011, San Antonio, TX.
this class are units that process hydrotreated 9 NPRA Q&A October 2000 Question 4: What single thing have
resid as well as straight-run resid. you done to improve the reliability of your FCC unit during the past
Processing heavily contaminated resid using year?.

10 PTQ Q4 2012 www.digitalrefining.com/article/1000656


Pat Walker is a Technical Services Fellow located at UOPs
headquarters in Des Plaines, Illinois. He is responsible for home Links
office support of FCC units and resid FCC units worldwide. He
holds a degree in chemical rngineering from the University of More articles from: UOP - A Honeywell Company
Illinois and is a registered professional engineer.
More articles from the following categories:
Raymond Peterman is Regional Service Manager for Honeywells
UOP. He holds an MBA from Pepperdine University and a degree Fluid Catalytic Cracking Petrochemicals
in chemical engineering from Northwestern University. He is Six Propylene Maximisation
Sigma Green Belt certified.

www.digitalrefining.com/article/1000656 PTQ Q4 2012 11