Increasing FCC Output by Oxygen Enrichment

MAXIMUM CAPACITY 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 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. OPTIMIZE CONVERSION 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 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 Base

4 Max. Yield O2 Enrich.

Control Parameters Reactor Fresh Feed Rate Temperature Feed Preheat Duty Regenerator Air Rate O2 Rate Dependent Parameters Reactor Coke Yield 430F EP Conversion Cat/Oil Ratio Regenerator O2 Enrichment Dilute Phase Temp. Dense Bed Temp. Flue Gas XS O2 Flue Gas CO2/CO Velocity Limit

M BPOD F MMBH

78.0 915 125.3

85.0 911 81.3

78.4 919 113

78.2 911 45.4

MSCFM MSCFM

130

128 3.7

132

133 3.3

WT% WT% W/W

4.3 69.4 5.8

4.5 67.9 5.8

4.5 68.9 6.1

4.9 72.2 6.6

% F F % V/V fps

21 1275 1263 0.2 4.7 3.2 Air

23.2 1265 1282 0.1 3.4 3.3 Wet Gas Compressor

21 1250 1260 0.2 2.7 3.2 Air

23.0 1290 1275 0.2 4.8 3.4 Wet Gas Compressor

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

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 1% Ar

Enriched air 100 Mscfm

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 O 2 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
FSH FIC PSL PC

FCC Process Alarms(2)

Gaseous Oxygen 50600 psig

(1)

FCCU Regenerator

FIC

TSH

FCCU Air Blower

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 Base case 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) 78,000 915 1,263 1,275 49.6 5.8 71.1 0.2 4.7 130.0 0 130.0 4.49 100.0 Supplemental blower 88,000 915 1,262 1,280 56.1 5.8 71.1 0.4 4.9 144.1 0 144.1 4.36 95.0 Air blower limit 88,000 915 1,268 1,285 55.2 5.7 71.1 0.4 4.9 130.0 2.5 132.5 4.31 93.0 Velocity limit 88,000 915 1,270 1,286 55.0 5.7 71.1 0.4 4.8 126.9 3.1 130.0 4.30 100.0

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 Base case 78,000 0 10.0 78,000 915 1,263 1,275 49.6 5.8 71.1 0.2 4.7 130.0 0 130.0 4.49 100.0 Supplemental blower 78,000 10,000 10.0 88,000 915 1,318 1,330 48.7 5.0 71.1 0.2 4.6 146.5 0 146.5 4.45 67.0 O2 enrichment 78,000 10,000 10.0 88,000 915 1,326 1,337 47.9 4.9 71.1 0.1 4.6 133.0 3.0 133.0 4.39 65.0

Gas oil feed (bpd) Resid feed (bpd) API gravity 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) O2 rate (Mscfm) Total gas (Mscfm) Coke (wt % tf) CRC (base = 100)

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

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. ECONOMICS The incentive for using FCC O enrichment is to obtain 2 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

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 Incremental gross profit, $MM/year 40 30 20 10 0

) OX (G en X) yg LO ox ( us en eo yg s ox Ga id 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

Hauled in liquid oxygen (LOX) 1 day5 years 48 weeks Higher Pipelined gaseous oxygen (GOX) 5 years15 years 924 months Lower

Length of supply commitment Construction period Price

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 Total feed (bpd) Feed with b.p. of 430F + (bpd) Main air blower (Mscfm) Oxygen enrichment ( Mscfm) Oxygen concentration (vol %) Conversion ( wt%) Average reactor temp. (F) Regen riser temp. (F) Regen bed temp. (F) Regen dilute phase temp. (F) Preheater duty ( MMBtu/h)
Base O2 Enrichment

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. 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

Increased capacity Trial #2

Base O2 Enrichment

12/08/82 12/09/82 12/11/82 78,360 76,774 131.5 0 21.0 68.9 919 918 1260 1284 113 78,216 77,881 132.3 3.4 23.0 72.2 911 914 1275 1302 45.4 77,966 77,681 130.0 0 21.0 69.4 915 940 1263 1275 125.3

12/10/82 84,967 84,635 128.0 3.7 23.2 67.9 911 920 1282 1291 81.3

*Reprinted from HYDROCARBON PROCESSING, September 1983 Copyright 1983 by Gulf Publishing Co., Houston, Texas. All rights reserved. Used with permission.