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since the refinery and petrochemical sites are closely integrated.
CEPSA’s La Rábida refinery has been producing high propyl-
ene yields for almost 25 years. Nonetheless, the refinery wished
to challenge the status quo and investigate if even better perfor- FIG. 1. FCCU feed composition.
12.0 22
11.5
21
11.0
20
10.5
Isobutylene, wt%
Propylene, %wt
10.0 19
9.5
18
9.0
Base catalyst 17 Base catalyst
8.5
New catalyst New catalyst
8.0 16
0 5 10 15 20 25 0 5 10 15 20 25
Furfural extracts on feed, vol% Furfural extracts on feed, vol%
FIG. 2. Propylene (left) and isobutylene (right) yields vs. proportion of FE in feed.
unconverted oil (UCO) from the hydrocracker mized liquefied petroleum gas (LPG) olefins.5, 6 This particular
and other nonconventional feeds in the FCC. catalyst allows for the production of highly olefinic naphtha by pro-
viding enhanced diffusion of feed molecules to pre-cracking sites
Laboratory testing. Prior to the commercial trial, CEPSA located on the external, exposed surface of highly dispersed zeolite
R&D performed a catalyst evaluation in its laboratory, compar- crystals. This results in higher bottoms conversion with high yields
ing catalysts from the incumbent and new catalyst suppliers.b of olefinic naphtha. The gasoline range olefins are then selectively
Fresh catalyst samples from each supplier were steam deacti- converted to LPG olefins by the ZSM-5 functionality.8
vated to simulate commercial ECat and then tested in a Davison
circulating riser pilot plant unit. Based on the results of this eval- Technical support service. While the catalyst was being
uation, the new catalyst was selected for a commercial unit trial.b tested, technical support services were provided to the refin-
In general, FCCUs typically produce around 4 wt% to 6 wt% ery. The package included site visits and logistical support,
propylene, depending on feed type, operating conditions and process and laboratory sample analysis and FCCU optimiza-
the FCC catalyst. By optimizing all these factors, propylene pro- tion using a number of proprietary tools.
duction can be increased up to 12 wt%.2, 4
To generate higher propylene yield, ZSM-5 additive is typi- Trial results. The La Rábida FCCU feed is a mixture of vacuum
cally added on top of the base catalyst, which can result in dilu- gasoil (VGO) and nonconventional feed components, such as
tion of the base catalyst activity. As a rule of thumb, every 5% UCO from the hydrocracker, Furfural extract (FE) from lubes
of non-FCC cracking material in the unit inventory reduces the processing and other low-value components. It is desirable to
FCC conversion by 1%. This is not a concern at low ZSM-5 ad- process all the UCO in the FCCU because recycling this in the
ditive levels, but at the high levels required to truly maximize hydrocracker tends to shorten catalyst cycle length.
propylene, it can become an issue. This can require higher fresh As the proportion of UCO in FCCU feed is increased, the pro-
catalyst addition rates to compensate for this activity dilution. portion of FE must also be increased to improve slurry viscosity
The catalyst under evaluation does not suffer activity dilution and heat balance in the FCCU. However, FE contains about 80%
because the ZSM-5 functionality is present in the base catalyst for- hydrocarbons with aromatic rings, and with the previously sup-
mulation. The presence of the ZSM-5 zeolite also allows for maxi- plied catalyst in the base case operation, it was difficult to convert
this material in the FCCU. In addition, the refractory FE con-
35 tributed to increased slurry yields. Historically at La Rábida, the
34 Base catalyst maximum amount of FE that could be processed in the FCCU
New catalyst
33 was constrained by the maximum slurry disposal to fuel oil.
32 The new catalyst delivered improved bottoms cracking perfor-
31
mance, allowing more of the FE aromatic side chains to be convert-
LPG yield, wt%
35
5
34
33 4
LCN, wt%
32
3
31
FIG. 4. Light-cracked naphtha (LCN) yield vs. ROT (left) and CEPSA R&D LCN olefins wt% for the La Rábida feed (right).
10.0 10.0
9.5 Base catalyst 9.5 Base catalyst
New catalyst New catalyst
9.0 9.0
8.5 8.5
Slurry yield, wt%
FIG. 5. Slurry yield vs. ROT (left) and proportion of FE in feed (right).
Plus, processing all the UCO in the FCCU helps improve cata- Hydrocarbon Processing, September 2011.
5
McLean, J., et al., “Distributed Matrix Structures: A Technology Platform for
lyst cycle length at the hydrocracker. The increased propylene yield Advanced FCC Catalyst Solutions,” NPRA Conference, AM-03-38.
supports CEPSA’s activity in the petrochemicals area, while the 6
Degnan, T. F., J. K. Chitnis and P. H. Schipper, “History of ZSM-5 fluid catalytic
increased C4 olefins yield minimizes the need for ethyl tertiary bu- cracking additive development at Mobil,” Microporous and Mesoporous Materials,
Vol. 35–36, pp. 245–252, 2000.
tyl ether unit feed imports. The improved conversion of low-value 7
Karpov, N. V., et al., “Case history: Optimization of FCC with multivariate statisti-
components, otherwise destined for fuel oil production, improves cal modeling,” Hydrocarbon Processing, September 2013.
the efficiency and profitability of the overall refinery. 8
McLean, J. and G. M. Smith, “Maximizing Propylene Production in the FCC
By challenging the status quo, CEPSA has improved the re- Unit: Beyond Conventional ZSM-5 Additives,” NPRA Conference, AM-05-61.
finery’s sustainability and economic performance.
JOSÉ MANUEL LLANES has been the FCC plant manager at CEPSA’s La Rábida
NOTES refinery since January 2010. He has a BS degree in chemistry and an MS degree
a Designed by Exxon Mobil in industrial safety. He joined CEPSA 15 years ago.
b BASF
BERTA ARAMBURU is a researcher responsible for the FCC area at the CEPSA
LITERATURE CITED Research Center. She studied chemical engineering at Madrid University and has
1
“Overview from conference: Maximizing propylene yields,” BASF Conference, been working for CEPSA for more than 10 years.
Frankfurt, Germany, June 19–20, 2013.
2
Shackleford, A., “FCC Benchmarking: Exploring Industry Trends and Creating MIGUEL ARJONA has been the FCC plant operations manager at CEPSA’s La
Paths Forward,” 10th FCC Forum, 2013. Rábida refinery since November 2011. He has an MS degree in industrial chemical
3
Larraz, L., et al., “Maximizing Propylene Production in an FCC unit,” 19th World engineering and a MS degree in industrial safety. He joined CEPSA seven years ago.
Petroleum Congress, Spain, 2008.
4
Knight, J. and R. Mehlberg,” Maximizing propylene from the FCC unit,” ELOISA SERRANO has been the FCC plant process engineer at CEPSA’s
La Rábida refinery since December 2011. She has an MS degree in industrial
89 and environmental engineering.
Base catalyst
87 MODESTO MIRANDA is BASF’s technical sales manager for CEPSA’s La Rábida
Test catalyst
refinery. He has a BS degree in engineering. Mr. Miranda has more than 20 years
Conversion corrected at 221, °C vol%
13 25
12 All data All data
La Rábida La Rábida
11 Test catalyst 20 Test catalyst
Test catalyst Test catalyst
ACE unit total LPG olefin yield, wt%
10
ACE unit C3= yield, wt%
9 15
8
7 10
6
5 5
4
3 0
60 62 64 66 68 70 72 74 76 78 80 60 62 64 66 68 70 72 74 76 78 80
ACE unit conversion, wt% ACE unit conversion, wt%
Eprinted and posted with permission to BASF Catalysts LLC from Hydrocarbon Processing
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