Improve FCCU Operations Using Well-Designed

and Properly Applied Chemical Programs.

Refineries continuously look for ways to minimise FCCU operating costs while dealing with changing
feed quality and maximising throughput.
Problems can range from fouling and catalyst fines contamination to high feed Nickel levels,
particularly in Resid-FCC processes. The variety and complexity of these problems requires an
accurate assessment of the system's mechanical, operational and chemical limitations before an
effective solution can be suggested.
Nalcos continuous R&D and many years of field experience have given insight in how to improve
FCCU operations with the use of well-designed and tailored chemical programs.
Deposit and stream analyses, proprietary test methods and process models are used to help
understand the root causes of the problems and to design the chemical programs that assist the
refiner to extend runlength, decrease maintenance and operating expenses while continuing to meet
product specifications.
The included case studies discuss the mitigation of FCCU slurry exchanger fouling, the removal of
NH4Cl deposits from the main column and overhead system and a detailed analysis of an RFCC Nickel
passivation program. In all these cases the state-of-the-art technology has been pushed to the limit.
The selected chemical programs, applied with the use of best practices and accurate monitoring
programs, have allowed the refiners to increase economic value and operating flexibility.

Introduction
Refinery fluid catalytic cracking unit (FCCU) engineers have to deal with a wide range of problems
when they look for ways to maximize the FCCU run lengths and minimize operational costs even as
feeds often get heavier and contain more contaminants.
The problems can range from slurry heat exchanger fouling, fractionator tower fouling due to coke
formation or NH4Cl salts, decant oil (DCO) catalyst fines contamination and high reactor coke and H2
production due to increased feed Nickel levels.
The following three case studies are examples of programs that have been implemented in the past
two years at different refineries, each with a distinctly different FCCU processing issue. In all the
cases, Nalco was asked by the refiners to survey their FCCU and propose a solution for their specific
problems. Every program involved the use of proprietary software, experience and specialty
chemicals. The outcome for each issue was a resolution of the problem and considerable cost savings
for the refiner.
The application of the Nalco programs have allowed the refiners to deal with the ongoing change in
feed qualities while maximising throughput and profit.

Case 1: FCCU Slurry Fouling Control

A US refiner was experiencing severe fouling of the FCCU slurry/feed exchangers. This impacted the
entire refinery profitability since the unit was running 5% below the design capacity of 80,000 bbp
due to higher than normal differential pressures (dP) across the slurry/feed exchangers. Maintenance
costs were also high due to the refiner having to clean an average of 2.5 slurry/feed exchangers per
month. Prior to Nalco involvement on the unit, it was typical for 22 slurry/feed exchangers to be
cleaned in an eight-month period.
Deposit samples were taken during one of the many slurry/feed exchanger cleanings and sent in for
analysis. The Nalco research laboratories in Sugar Land, Texas determined that the primary cause of
the fouling was the result of coking (indicated by a high carbon-to-hydrogen ratio) in the bottom of
the fractionator. The analysis also showed evidence of inorganic components (catalyst fines)
deposited with the coke. In addition to deposit analyses, a proprietary Nalco test method(1) was used
to analyze samples of the FCCU slurry. This technique is used to measure the fouling tendency of the
slurry oil. A recommendation was made to inject a coke suppressant/inorganics dispersant into the
fractionator tower and an organics dispersant was selected to prevent the agglomeration and
deposition of polynuclear aromatics in the slurry exchangers.
Proper application of antifoulant chemicals is the key to success. As illustrated in Figure 1, the coke
suppressant/inorganics dispersant was added into the slurry return line to the main fractionator in
order to prevent coke formation in the fractionator bottoms. The temperature of the fractionator
bottoms ranged from 357 to 368C.
An organics dispersant was added to the suction of the slurry pumps from the bottom of the
fractionator. This allowed the chemical to react with and disperse polynuclear aromatic compounds
through the exchangers.

Figure 1

The antifoulant program was monitored by tracking the exchanger pressure drops, and with
Monitor modeling of the exchanger U-values and fouling factors. Since the start-up of the program,
the exchanger dPs steadied and unit throughput was recovered back to design levels. Overall, the
exchanger run-lengths increased from 11 days to one year. Figure 2 shows the historical exchanger
cleanings before and after the Nalco fouling control treatment was implemented.

Figure 2
The economics of the antifoulant program involved the following factors: throughput limitations,
cleaning costs and lost opportunity in terms of maintenance and production issues. The total profit
increase for the refinery by implementing this program is estimated at $8 M/year.

Case 2: FCCU Fractionator NH4Cl Fouling Control

Deposition of inorganic salts in FCCU main fractionator towers is a common cause of operating
problems and lost profits(2). They tend to form and deposit in the mid-to-upper sections of the main
column and side stream pumparound exchangers (Figure 3). If not removed, these salts can
accumulate and cause a number of significant problems maintaining optimal tower operation and
the deposits can affect the operation of the entire FCC unit.

Figure 3
Partly due to industry compliance with new gasoline sulphur specifications there has been a growing
trend in the occurrence of FCCU main fractionator salt fouling.
The majority of the full-range FCCU gasoline sulphur is contained in the heavy naphtha (HN) fraction.
To meet the European Community gasoline sulphur specifications, many refiners have installed a HN
draw on the fractionator. This allows them to hydrotreat the HN for sulphur removal, without
saturating the olefins contained in the light cracked naphtha (LCN).
Installation of a HN draw allows the refiner to reduce the tower top temperature. If significant
quantities of chlorides are present in the vapour phase solid NH4Cl salts can form and build up.
FCCUs that have Atmospheric or Vacuum residue as part of the feed or RFCCs typically have a
considerable level of chlorides in the vapours.
A 15,800 bpd European RFCC was experiencing severe fractionator fouling and operational problems
due to the formation of NH4Cl salts in the fractionator top section. The NH4Cl salt deposition had a
negative impact on the fractionation efficiency between the HCN and HN fractions. The target gap
between the HCN 95% volume point and the HN 5% volume point was 10 C but without treatment
this was a negative value (figure 4).

Salt Dispersant Monitoring

195

180

160

190
140

185

180

100

80

175

D86 C

Dosage ppmv

120

60

170
40

165
20

160

04/04/08

02/04/08

Dosage dispersant B ppmv

31/03/08

29/03/08

27/03/08

25/03/08

23/03/08

21/03/08

19/03/08

Dosage dispersant A ppmv

5vol% D86 HN C

Salt Dispersant Monitoring

25

70

20
15

65

60

5
0

55

-5

Gap / Overlap

Flash C

10

-10
50

-15
-20

45

-25
04/04/08

02/04/08

31/03/08

29/03/08

27/03/08

25/03/08

23/03/08

21/03/08

19/03/08

Flash HN C

Gap(-)/Overlap(+)

Figure 4
The refinery was performing tower water washings to remove NH4Cl salts by lowering the
fractionator top temperature enough to condense liquid water on the trays. The water and dissolved
salts were then removed through the HN product draw. The tower water washings led to significant
production losses. During water washing, the unit feed rate had to be reduced and HN and LCO had
to be sent to slop.
After a Nalco survey, a salt dispersant treatment (dispersant A) was started and the fractionator
fouling rate was reduced. In a later stage a second intermittent cleaning treatment (dispersant B)
was added and this completely eliminated the need for a tower washing. The estimated savings for
the refinery are in the range of $2 M/year.

Case 3: FCCU Nickel Passivation

Contaminant Nickel can enter with the feed to the FCCU bound up in large organo-metallic
compounds. These compounds are typically present in Atmospheric or Vacuum Residue or in deep
cut HVGO. They begin to break down thermally and catalytically in the riser, where the Nickel is
liberated and deposits on the cracking catalyst. This fresh Nickel is very catalytically active and will
cause immediate dehydrogenation of the hydrocarbon feedstock producing hydrogen and coke.
Besides causing a direct loss of valuable liquid products such as gasoline and light olefins, the excess
hydrogen and coke make causes operational limitations that further reduce conversion and FCC feed
rates. The economic penalties associated with excess contaminant metal activity are quite significant.
A new Middle East RFCC processing 75,000 bpd Atmospheric Residue was suffering from high dry gas
make. The feed metals content was very high with an average 13 ppm Nickel and up to 6000 ppm
Nickel on the equilibrium catalyst (E-cat). The unit was Wet Gas Compressor limited. Several Nickel
tolerant Catalysts types and vendors had been tried but the unit kept operating with significant
limitations.
Beginning in 2008, after an evaluation with Nalco, it was decided to select a Nickel Passivation Plus
Program. This was based on the experience that many refiners using Nickel tolerant catalysts are
also using a Nickel Passivation plus program because this is providing further protection against the
detrimental effects of Nickel and gives them greater flexibility(3).
Injection facilities were installed according to Nalco best practice and the passivator was injected in
the feed to the riser with an initial high baseload dosage.
H2 Make and Conversion
H2

conversion
86.00

30.00

84.00
25.00
82.00
20.00

76.00
10.00
74.00
5.00

Start Nalco Passivation Plus

0.00

72.00

70.00

date

Figure 5

78.00

15.00

22
/0
2 3 2 /2
/0 0 0
2 4 2 /2 8
/0 0 0
2 5 2 /2 8
/0 0 0
2 6 2 /2 8
/0 0 0
2 7 2 /2 8
/0 0 0
2 8 2 /2 8
/0 0 0
2 9 2 /2 8
/0 0 0
0 1 2 /2 8
/0 0 0
0 2 3 /2 8
/0 0 0
0 3 3 /2 8
/0 0 0
0 4 3 /2 8
/0 0 0
0 5 3 /2 8
/0 0 0
0 6 3 /2 8
/0 0 0
0 7 3 /2 8
/0 0 0
0 8 3 /2 8
/0 0 0
0 9 3 /2 8
/0 0 0
1 0 3 /2 8
/0 0 0
1 1 3 /2 8
/0 0 0
1 2 3 /2 8
/0 0 0
1 3 3 /2 8
/0 0 0
1 4 3 /2 8
/0 0 0
1 5 3 /2 8
/0 0 0
1 6 3 /2 8
/0 0 0
1 7 3 /2 8
/0 0 0
1 8 3 /2 8
/0 0 0
1 9 3 /2 8
/0 0 0
2 0 3 /2 8
/0 0 0
2 1 3 /2 8
/0 0 0
2 2 3 /2 8
/0 0 0
2 3 3 /2 8
/0 0 0
2 4 3 /2 8
/0 0 0
2 5 3 /2 8
/0 0 0
2 6 3 /2 8
/0 0 0
2 7 3 /2 8
/0 0 0
2 8 3 /2 8
/0 0 0
2 9 3 /2 8
/0 0 0
3 0 3 /2 8
/0 0 0
3 1 3 /2 8
/0 0 0
0 1 3 /2 8
/0 0 0
4/ 8
20
08

nm3/m3 feed

80.00

As can be seen in Figure 5, the dry gas make and delta coke responded immediately with a sharp
decrease. The refinery immediately used the spare capacity to increase the conversion by several
percent (Figure 5) and the unit throughput by more than 10% (Figure 6). The estimated net result for
the refinery is a profit increase of $60 M/year.
Feedrate m3/h
AtRes Feed Flow Rate (Raw), m3/hr
500
450
400
>10% increase
350

m3/h

300
250
200
150
100

Start

Nalco Passivation Plus

50

22
/0
23 2/2
/0 0 0
24 2/2 8
/0 0 0
25 2/2 8
/0 0 0
26 2/2 8
/0 0 0
27 2/2 8
/0 0 0
28 2/2 8
/0 0 0
29 2/2 8
/0 0 0
01 2/2 8
/0 0 0
02 3/2 8
/0 0 0
03 3/2 8
/0 0 0
04 3/2 8
/0 0 0
05 3/2 8
/0 0 0
06 3/2 8
/0 0 0
07 3/2 8
/0 0 0
08 3/2 8
/0 0 0
09 3/2 8
/0 0 0
10 3/2 8
/0 0 0
11 3/2 8
/0 0 0
12 3/2 8
/0 0 0
13 3/2 8
/0 0 0
14 3/2 8
/0 0 0
15 3/2 8
/0 0 0
16 3/2 8
/0 0 0
17 3/2 8
/0 0 0
18 3/2 8
/0 0 0
19 3/2 8
/0 0 0
20 3/2 8
/0 0 0
21 3/2 8
/0 0 0
22 3/2 8
/0 0 0
23 3/2 8
/0 0 0
24 3/2 8
/0 0 0
25 3/2 8
/0 0 0
26 3/2 8
/0 0 0
27 3/2 8
/0 0 0
28 3/2 8
/0 0 0
29 3/2 8
/0 0 0
30 3/2 8
/0 0 0
31 3/2 8
/0 0 0
01 3/2 8
/0 0 0
4/ 8
20
08

date

Figure 6
Conclusion
The problems addressed in this paper are challenges that refiners are facing daily. As the global
economical situation is becoming more challenging and the crude qualities continue to worsen,
refiners will need to continue operating without sacrificing throughput, with minimum upsets and
operational costs. The cases discussed demonstrate how the use of chemical programs can assist the
refiners in extending run length, decreasing maintenance and operating expenses while continuing to
meet product specifications. The results are increased safety, flexibility and profitability at a lower
cost of operation.

References
1
2
3

Kailash N. Sawhney 2002 AIChE Spring Meeting The FCCU Slurry Loop Fouling
Mitigation
William F. Minyard, 31/05/2000 Solutions to Fluid Catalytic Cracker Main Fractionator
Salt Fouling
The FCC Network News June-July 2000 Volume 4, page 3