Increasing FCC Output by Oxygen

Enrichment
MAXIMUM CAPACITY

OPTIMIZE CONVERSION

The objective is to maximize feed rate using O2

enrichment. Starting at the base operating conditions
limited by air availability, GOX is added to the
regenerator. At the same time FCC feed is increased to
produce more coke and consume excess O2. As feed is
added, the reactor temperature is maintained by
increasing catalyst circulation rate.
The increased
regenerator dense bed temperature results in a lower
cat/oil ratio and consequently lower conversion than the
base case. To offset this, feed preheat is reduced and
catalyst circulation is increased to hold reactor
temperature constant. All these moves are balanced
when the CO2/CO ratio, excess O2, and reactor
temperature are the same as the base case, resulting in
nominally the same regenerator dense bed temperature,
regenerator gas velocity, and feed conversion. The feed
rate increase is nearly proportional to the increase in O2
available for coke combustion. The ultimate limit on
capacity is usually product recovery; specifically, the wet
gas product compressor.

The objective is to optimize conversion by maximizing

catalyst/oil ratio at the optimum reactor temperature
while maintaining constant feed rate. Starting at the
base operation conditions, GOX is added to the
regenerator and feed preheat is reduced. At the same
time, catalyst circulation is increased to control reactor
temperature, decreasing the regenerator temperature.
The coke yield and conversion increase as reactor
temperature and cat/oil ratio are raised. As more coke
is burned, the CO2/CO ratio in the flue gas falls and the
regenerator temperature rises. All of these moves are
balanced when the CO2/CO ratio, excess O2, and reactor
temperature are the same as the base case, resulting in
nominally the same regenerator temperature and gas
velocity and increased conversion at constant feed rate.

The effect of O2 enrichment for maximum feed rate with

the regenerator in partial CO combustion is shown in
Cases 1 and 2. At 23% O2, wet gas compressor
capacity limits further feed rate increases.
The Case 2 results show a small loss in conversion and
an increase in regenerator temperature compared to
Case 1. Both of these can be offset by slightly reducing
feed rate (200300 BPD) and increasing catalyst
circulation. This would raise the reactor temperature and
increase the CO2/CO ratio to the base case. At 23% O2,
no increase in CO afterburning was observed, and the
coke on regenerated catalyst (CRC) remained constant.

The coke yield increase is nearly proportional to the

increase in available O2; and conversion can be related to
coke yield. The ultimate limit on conversion (from
maximizing cat/oil ratio) is usually product recovery
(specifically the wet gas product compressor) or
minimum feed preheat temperature (resulting in high
regenerator temperatures).
The effect of O2 enrichment for maximizing conversion
with the regenerator in partial CO combustion is shown
in Cases 3 and 4. At 23% O2, the wet gas compressor
limits further conversion increases, since no more gas
make can be handled. No increase in CO afterburn was
observed, and the CRC remained constant.
The optimal unit operation probably lies in the middle of
the maximum feed and conversion tests. That is, more
product barrels can probably be made at less than max
feed and conversion using oxygen enrichment.

FCC O2 ENRICHMENT TESTS

DECEMBER 1982
Partial Combustion Operation
Straight Run Gas Oil Feed

Case

1
2
Max. Capacity
Base

O2 Enrich.

3
7/8

4
Max. Yield

Base

O2 Enrich.

Control Parameters
Reactor
Fresh Feed Rate
Temperature
Feed Preheat Duty

M BPOD
F
MMBH

78.0
915
125.3

85.0
911
81.3

78.4
919
113

78.2
911
45.4

Regenerator
Air Rate
O2 Rate

MSCFM
MSCFM

130

128
3.7

132

133
3.3

Dependent Parameters
Reactor
Coke Yield
430F EP Conversion
Cat/Oil Ratio

WT%
WT%
W/W

Regenerator
O2 Enrichment
Dilute Phase Temp.
Dense Bed Temp.
Flue Gas XS O2
Flue Gas CO2/CO
Velocity

%
F
F
%
V/V
fps

Limit

Feed Quality
Straight Run Vacuum Gas Oil
Boiling Range:
3501000F
Con Carb.:
0.30.4 WT%

4.3
69.4
5.8

4.5
67.9
5.8

4.5
68.9
6.1

4.9
72.2
6.6

21
1275
1263
0.2
4.7
3.2

23.2
1265
1282
0.1
3.4
3.3

21
1250
1260
0.2
2.7
3.2

23.0
1290
1275
0.2
4.8
3.4

Wet Gas
Compressor

Air

Air

Wet Gas
Compressor

RESULTS FROM ARCOS EXPERIENCE IN ITS

HOUSTON REFINERY SHOW HOW TO STRETCH THE
CATALYTIC CRACKING UNIT'S THROUGHPUT OR
HELP THE UNIT HANDLE HEAVIER FEED*
D. P. Bhasin and M. S. Liebelson,
Air Products and Chemicals, Inc., Allentown, PA,
and G. J. Chapman, Arco Petroleum Products Co.,
Houston
To increase the capacity of fluid catalytic cracking
(FCC), refiners must contend with process limitations,
such as insufficient coke burning in the catalyst
regenerator. Coke burning can be limited by: air blower
capacity, regenerator superficial velocity, waste heat
boiler velocity, electrostatic precipitator loading or
regenerator temperature. Oxygen enrichment of the
regenerator air provides a way around the blower and
velocity limits while remaining within regenerator
temperature constraints.
This article reviews oxygen enrichment techniques,
operational procedures and associated economic
benefits. Concepts are illustrated via reference to a
successful oxygen enrichment demonstration program at
Arco's Houston, Texas, refinery. Since regenerator
temperature is a common limitation, the effects of O2
enrichment on the FCCU heat balance are analyzed
using computer model simulations.
OXYGEN ENRICHMENT
Before discussing a specific commercial unit, let us
review the operational and safety issues associated with
FCC O2 enrichment. Oxygen enrichment is suitable:
When the investment in an air blower cannot be
justified because of the temporary nature of the
additional air requirement (e.g., for summer months or
short-term peak loading),
On an interim basis to increase capacity until a larger
blower can be installed during a scheduled turnaround,
When an increase in the FCC's throughput would
require substantial investment because of increased
regenerator velocity, inadequate heat recovery or
increased particulate emissions.
The effects of FCC O2 enrichment on regenerator air flow
for two different process limitations will be considered. In
the first case (Fig. 1) where air blower capacity is a
bottleneck, pure oxygen can be injected into the blower
discharge without modifying the air blower or shutting
down the FCC unit. The total gas flow entering the
regenerator increases somewhat. However, since no
nitrogen is added with the oxygen, the increase is only

one-fifth of that when additional air blower capacity is

installed.
In the other case (Fig. 2), where flue gas or superficial
velocity in the regenerator is a limitation, one can reduce
the inlet air flow and inject pure oxygen into the blower
discharge without shutting down the unit. Again, no
blower modifications are necessary. In this case, part of
the nitrogen in the original air flow is replaced by pure
oxygen. Therefore, more oxygen is available for coke
combustion without increasing the flue gas volume. In
this way, oxygen enrichment reduces catalyst carryover
and maintains velocities in the regenerator vessel and
downstream heat recovery system.
5.3 Mscfm O2

21% O2
Air
100 Mscfm 78% N
2
1% Ar

25% O2

Enriched air
74% N2 105.3 Mscfm
1% Ar

Fig. 1 For a blower limitation, adding oxygen to 100 Mscfm

of air blower output (total 105.3 Mscfm) has oxygen
equivalent to 125.2 Mscfm of unenriched air.
5.1 Mscfm O2

21% O2
Air
94.4 Mscfm 78% N
2
1% Ar

25% O2
74% N2

Enriched air
100 Mscfm

1% Ar

Fig. 2 For a regenerator velocity limitation, reducing air

blower volume so that air plus oxygen remains 100 Mscfm
has the oxygen equivalent of 119 Mscfm of unenriched air.

The safety issues involved with oxygen in refinery

environments, and FCC O2 enrichment in particular, are
of great concern due to the consequences of an
uncontrolled oxygen injection into the regenerator air. In
addition to providing monitoring and control of oxygen
flow during normal operation, an oxygen flow control
system should ensure automatic shutoff of oxygen in the
event of an upset condition. Fig. 3 illustrates a typical
oxygen flow control system for FCC enrichment.
Redundant safety interlocks are used to ensure that O2
concentration in the regen air is always below 27
percent. For O2 concentrations above 27 percent, a
hazards risk analysis should be conducted to ensure
materials and process compatibility.
QUESTIONS WITH ANSWERS
A common concern of refiners evaluating the use of
oxygen for FCC enrichment is what effects oxygen will

have on regenerator temperature. There are three parts

to this question:
Will regenerator temperature rise if oxygen is used to
expand gas oil capacity?
Will regenerator temperature rise if oxygen is used to
expand resid capacity?
Will individual catalyst particles see temperatures
higher than measured bed temperatures?
In a heat balanced FCCU which is not air blower or
velocity limited, an increase in gas oil charge at constant
conversion is accompanied by an increase in catalyst
circulation rate, an increase in air rate, and little or no
change in regenerator temperature. The heat evolved by
the additional coke combustion is removed by the
increased catalyst and air flows. Most of the heat is
transferred to the catalyst with only 1530% leaving with
the flue gas. When oxygen enrichment is used, the
incremental nitrogen which would normally be present in
the regenerator gas is absent. The loss of this additional
heat sink produces a small increase in regenerator
temperature.
The magnitude of the increase is
dependent on the extent to which nitrogen diluent is

reduced. The temperature increase is larger when air

blower flow is cut back to maintain or lower regenerator
velocities. In order to calculate the rise in regenerator
temperature, an iterative procedure must be used since
temperature rises are accompanied by decreased
catalyst circulation, less coke make and less heat
evolved. The three temperature issues are discussed in
the examples that follow.
GAS OIL
Table 1 compares operation with O2 enrichment versus a
supplemental blower for an increased gas oil operation at
constant conversion and preheat. The results were
obtained using the Air ProductsHoudry FCC computer
model and base case data from Arco's Houston, Texas,
FCCU. The computer model was first calibrated with four
of the detailed yield analyses performed during the Arco
test program. Compared to a supplemental blower,
the dense and dilute phase temperatures increase by
6-8F and 56F, respectively, when oxygen enrichment
is used to increase gas oil throughput from 78,000 bpd to
88,000 bpd, a 13% increase in capacity. Temperature
increase is slightly higher for the velocity limited case
due to the requirement that total regenerator gas flow
rate be held constant at 130,000 scfm.

O2
System
S/D

FCC
Process
Alarms(2)

FSH
FIC
PSL
PC

Gaseous
Oxygen
50600 psig

FCCU
Regenerator
(1)

FIC

FCCU
Air Blower

TSH

Proprietary
Oxygen
Diffuser

Notes:
1. Safety pressure setting based on FCC air line design pressure.
2. Two typical process alarms are low air line pressure and high regenerator dense bed temperature

Table 1
Model Prediction: Oxygen enrichment vs.
supplemental blower for increased gas oil feed
O2 enrichment

Gas oil feed (bpd)

Temperatures (F)
Reactor
Rgn. dense
Rgn. dilute
Cat. circ. (tpm)
Cat/oil (lb/lb)
Conversion (v%)
Rgn. orsat (v%)
O2
CO2/CO
Air rate (Mscfm)
O2 rate (Mscfm)
Total regen gas
(Mscfm)
Coke (wt % tf)
CRC (base = 100)

Base
case

Supplemental
blower

Air
blower
limit

Velocity
limit

78,000

88,000

88,000

88,000

915
1,263
1,275
49.6
5.8
71.1

915
1,262
1,280
56.1
5.8
71.1

915
1,268
1,285
55.2
5.7
71.1

915
1,270
1,286
55.0
5.7
71.1

0.2
4.7
130.0

0.4
4.9
144.1

0.4
4.9
130.0

0.4
4.8
126.9

2.5

3.1

130.0
4.49
100.0

144.1
4.36
95.0

132.5
4.31
93.0

130.0
4.30
100.0

RESID
When injecting oxygen to increase resid cracking
capacity, regenerator temperature will increase
significantly beyond the rise seen with gas oil. This
increase is primarily due to the high levels of catalytic
and feed coke in the resid feedstock and not due to
oxygen injection per se. Based upon isothermal pilot
plant tests, it is a mistake to conclude that adding resid
to a heat balanced FCCU will raise overall coke yield.
Actually, in an FCCU with no external means of heat
removal such as steam coils or catalyst coolers, overall
coke yield is fixed by the unit heat balance at a constant
reactor temperature. If the enthalpy required to crack
resid is equal to that required for gas oil, overall coke
yield per barrel will remain approximately constant,
regardless of feedstock. The effect of adding resid is an
increase in feed coke and a decrease in catalyst
circulation coke. The net effect of this change is a
reduction in catalyst-to-oil ratio, which at constant overall
coke yield and reactor temperature, raises regenerator
temperature. The increased regenerator temperature
increases the coke burning rate, thus reducing carbon on
regenerated catalyst (CRC). The conversion decrease
caused by lower catalyst-to-oil ratio may be offset by the
selectivity increase due to reduced CRC. Whether or not
these opposing effects allow for a constant conversion
operation depends on specific unit characteristics and
the CRC level before adding resid.
Due to the interaction of many FCC variables, the
computer model is used again to compare the same

base case with an operation where 10,000 bpd of

incremental resid is added to the feed. The resid has a
70% higher laboratory (i.e., isothermal) coke yield and
slightly lower laboratory conversion than the gas oil.
Table 2 illustrates the output of the computer simulation
model at constant conversion for an air blower limited
case where first, supplemental air blower capacity is
added to burn the additional coke and second, where
oxygen enrichment is used. Regenerator temperature
rise is greater than 50F for both cases. The reduction of
the nitrogen heat sink with oxygen enrichment causes
an additional 8F increase in dense phase temperature
when compared to a supplemental blower. In this
analysis, conversion is maintained by the increased
selectivity of the FCC catalyst at lower CRC levels.
Table 2
Model Prediction: Oxygen enrichment vs.
supplemental blower for increased resid feed
Air blower limit

Gas oil feed (bpd)

Base
case
78,000

Supplemental
blower
78,000

O2
enrichment
78,000

Resid feed (bpd)

API gravity

0
10.0

10,000
10.0

10,000
10.0

Total feed
Temperatures (F)
Reactor
Rgn. Dense
Rgn. dilute
Cat. circ. (tpm)
Cat/oil (lb/lb)
Conversion (v%)
Rgn. orsat (v%)
O2
CO2/CO
Air rate (Mscfm)

78,000

88,000

88,000

915
1,263
1,275
49.6
5.8
71.1

915
1,318
1,330
48.7
5.0
71.1

915
1,326
1,337
47.9
4.9
71.1

0.2
4.7
130.0

0.2
4.6
146.5

0.1
4.6
133.0

O2 rate (Mscfm)
Total gas (Mscfm)
Coke (wt % tf)
CRC (base = 100)

0
130.0
4.49
100.0

0
146.5
4.45
67.0

3.0
133.0
4.39
65.0

CATALYST PARTICLE TEMPERATURE

The last temperature issue to be addressed is the effect
that oxygen enrichment has on catalyst particle
temperatures. This question has been raised primarily
where enrichment is contemplated on FCC units of a
side-by-side design where combustion air and spent
catalyst are mixed in the regen riser. The concern is
that the increased oxygen partial pressure in the riser
will cause excessive catalyst temperatures before the
spent catalyst enters the regenerator bed. Once the
catalyst enters the bed, the heat of combustion is
absorbed in the larger quantity of catalyst that is present

in the dense phase. Whether or not excessive catalyst

temperatures will result from enriching side-by-side units
is a site-specific question which can best be answered
by a well-instrumented test program, such as the one at
Arco, that closely monitors regen riser and regen grid
temperatures. At Arco, no significant increase in regen
riser temperature was observed.

oxygen plant and then transported via pipeline to the

refinery. Energy and transport costs make LOX more
expensive than GOX on a unit cost basis. However, as
illustrated in Table 3, this price disadvantage may be
offset by a shorter required supply period and a quicker
response time.

50

The incentive for using FCC O2 enrichment is to obtain

an incremental gas oil or resid charge to the FCCU by
increasing
regenerator
coke
burning
capacity.
Enrichment is economical if:
The value added gained from additional throughput is
larger than the cost of oxygen;
Alternative modifications to regeneration equipment or
the air blower are either more expensive than the present
value cost of oxygen or require substantially longer lead
time or downtime when compared with O2.
For example, in a situation where the regenerator vessel,
electrostatic precipitator or the waste heat boiler is at a
velocity limit, additional capacity obtained with increased
air flow must be accompanied by expensive equipment
modifications. Oxygen enrichment allows increased
capacity at constant velocities and makes economic
sense on a long-term basis. On the other hand, if an air
blower limit exists with no other equipment limitations,
installing supplemental blower capacity will, in general,
be less expensive than oxygen enrichment on a longterm basis. However, in this latter situation, oxygen
could be used economically on an interim basis until a
new blower is installed.
The incremental gross profit obtained from 10,000 bpd
of incremental FCC feed for combinations of product
value added and oxygen price is shown in
Fig. 4. The chart is based on a fixed 5% overall coke
yield on feed and therefore assumes either additional gas
oil feed or resid cracking with no external source of heat
removal. For example, if the value added in upgrading an
incremental 10,000 bpd of gas oil feed to FCC products
is $5/bbl, the incremental gross profit after deducting
oxygen cost is between $9MM and $14MM per year.
The spread in incremental gross profits is a function of
the oxygen supply mode. For relatively small volumes or
for short-term requirements, oxygen is more
economically supplied as a liquefied gas. Liquid oxygen
(LOX) is transported by truck to the refinery where it is
stored in insulated tanks. The LOX is then vaporized
with steam or air for injection into the blower discharge
line. For larger requirements, gaseous oxygen (GOX) is
generated at an Air Products owned and operated

Incremental gross profit,

$MM/year

ECONOMICS

40
30
20
10
0

X)
O
G
n(
e
g
X)
O
xy
L
o
(
s
en
ou
g
e
y
s
ox
Ga
d
i
u
Liq

1 2 3 4 5 6 7 8 9 10 11 12 13

Value added, $/bbl

Gas Oil

Resid

Fig. 4 These incremental gross profit data are based on

being able to add 10 Mbpd additional feed.

COMMERCIAL RESULTS
An air blower limitation at the 75,000 bpd Sinclair
designed FCC unit at Arco's Houston, Texas, refinery
prevented feed rate increases. The unit is scheduled for
a turnaround in 1985 that will allow for debottlenecking
the blower, but the incentive to increase production
during the interim period was strong enough to consider
oxygen enrichment as a short-term alternative. The Arco
FCCU is a side-by-side design where all of the
combustion air is combined with catalyst in the
regenerator riser line. A major question was whether or
not higher oxygen partial pressure would cause an
increased burning rate in the regen riser resulting in
excessive catalyst particle temperatures, Because of
this concern, it was decided that a well-instrumented
test program be undertaken before installing oxygen
enrichment on a permanent basis. The test run was
designed to safely answer the following questions:
Will oxygen enrichment cause excessive regen and
regen riser temperatures?
Will oxygen enrichment improve FCC yields?
How much extra feed can be processed using oxygen
enrichment?

Table 3
Liquid vs. gaseous oxygen supply tradeoffs

Length of supply
commitment
Construction period
Price

Hauled in
liquid
oxygen (LOX)
1 day5 years

Pipelined
gaseous
oxygen (GOX)
5 years15 years

48 weeks
Higher

924 months
Lower

A thermocouple was hot-tapped in the regen riser and

this temperature was closely monitored along with points
under the grid. The yield benefit was evaluated by
attempting to burn more coke at constant feed rate and
cat/oil ratio, thereby reducing carbon on regenerated
catalyst (CRC). The feed benefit was obtained by
burning more coke at constant CRC and cat/oil ratio,
thereby raising throughput.
Oxygen enrichment into the FCCU was implemented
within four weeks from the time of a go-ahead decision.
Liquid oxygen for the test was transported to the refinery
at a rate of ten tanker trucks per day. The LOX was
pumped into two mobile customer stations which acted
as surge tanks for the varying flow rates. Each mobile
customer station contained a 3,000-gallon tank and a
steam vaporizer capable of gasifying 125 Mscfh of
oxygen. Oxygen flow was controlled via a flow control
and instrumentation system incorporating redundant
safety interlocks to prevent high oxygen concentrations
in the blower discharge line. Oxygen injection was
accomplished by hot-tapping a 6-in. nozzle on the air
blower discharge line and inserting a 4-in. diffuser
designed to prevent impingement of unmixed oxygen on
the carbon steel blower line and downstream flow
components.

and conversion, but this was not economically significant

at the time due to the small differential price between
gasoline and heating oil. In Trial 2, additional gas oil
capacity of 6,950 bpd was obtained with the addition of
222 Mscfh of oxygen at a 23.3% enrichment level. The
conversion decrease from 69.4 wt% to 67.9 wt% was
due to the lower reactor temperature and weight balance
corrections to the data and not due to O2 enrichment. In
Trial 2 regenerator temperature increased by 19F and
preheater duty was cut by 44 MMBtu/h.
Because of the test success, Arco will use oxygen,
when needed, until the next turnaround when blower
modifications might be implemented.
Table 4
Arco test results
Increased yield
Trial #1
Test run
Date

Base

O2
Enrichment

Increased capacity
Trial #2
Base

12/08/82 12/09/82 12/11/82

O2
Enrichment

12/10/82

Total feed (bpd)

Feed with b.p. of 430F + (bpd)
Main air blower (Mscfm)

78,360
76,774
131.5

78,216
77,881
132.3

77,966
77,681
130.0

84,967
84,635
128.0

Oxygen enrichment ( Mscfm)

Oxygen concentration (vol %)

0
21.0

3.4
23.0

0
21.0

3.7
23.2

Conversion ( wt%)
Average reactor temp. (F)
Regen riser temp. (F)
Regen bed temp. (F)
Regen dilute phase temp. (F)

68.9
919
918
1260
1284

72.2
911
914
1275
1302

69.4
915
940
1263
1275

67.9
911
920
1282
1291

Preheater duty ( MMBtu/h)

113

45.4

125.3

81.3

A safety and operational training session was given to all

unit operators to ensure that correct operating
procedures were followed.
The test program demonstrated that with oxygen,
7,000 bpd of additional gas oil feed could be charged to
the FCCU at constant conversion and without excessive
regenerator temperature. Eight detailed yield tests were
performed over a two-week period. The FCCU was linedout for 24 hours before each unit evaluation and data
comparison were made. Analyses were performed within
a one-day span in order to minimize any unnoticed
feedstock or unit changes. Table 4 compares results for
test runs before and after oxygen injection,
demonstrating increased yield (Trial 1) and increased
capacity (Trial 2). In Trial 1, CRC could not be reduced
with oxygen enrichment due to catalyst flow problems
which were unrelated to oxygen injection. There was a
1.5% increase in gasoline yield from the higher cat/oil

*Reprinted from HYDROCARBON PROCESSING, September 1983

Copyright 1983 by Gulf Publishing Co., Houston, Texas.
All rights reserved. Used with permission.