Maximising yields and profits from the

FCC unit
Comparative additive trials demonstrated a gain in petrochemicals output and profit
from an integrated refinery’s FCC unit

Silviu Serban, Chuck Ekeocha, Udayshankar Singh and Bani Cipriano Grace Refining Catalyst Technologies

T
he growth in demand for fuels worldwide is pro- crude oil, bringing annual output to around 22 million
jected to slow down as a result of the electrifica- tonnes of refined petroleum products, including 200 000
tion of the vehicle fleet and maturing of advanced tonnes of high purity propylene.
economies. On the other hand, demand for petrochem- The key objectives of the SATORP FCC unit are high
icals is still on a growth trajectory. Integrating petro- conversion and high yield of light olefins, including C3=
chemical production with their operations provides and C4=s. The feed is very light and therefore easy to
refineries an opportunity to profit from this growth crack, but it is very low in Concarbon and metals which
trend and ultimately avoid risk of closure in the face results in reduced delta coke and regenerator tempera-
of slowing demand. This trend of integration between ture. Consequently, combining a catalyst that closes the
refining and petrochemicals is well under way: in the heat balance with an optimal ZSM-5 additive to max-
past several years, megaprojects were announced in imise light olefins is critical. Additionally, due to the
China, in which the yield of petrochemicals from each nature of the feed and very high unit conversion, the
barrel of crude is slated to reach ~40%.1 New projects riser outlet temperature (ROT) is depressed to below
have been announced, most notably by Saudi Aramco, 505°C which imposes further challenges.
that seek to push this yield up further.2 The benchmarking plots in Figure 1 show SATORP’s
At Grace, we believe the fluid catalytic cracking FCC unit compared with other FCC units in the EMEA
(FCC) unit facilitates the transition of refineries from region in terms of key parameters: feed specific gravity,
fuels to a focus on petrochemicals. The reason for this ROT, and C3= and total C4= yields. The SATORP unit
is that the FCC unit generates the highest yield of light operates near the lowest in terms of feed specific grav-
olefins, specifically propylene, compared to other units ity and ROT and near the highest in terms of C3= and
in the refinery. Therefore, the company’s focus is on C4= yields.
developing new technologies that allow refiners seek- To achieve this performance, Grace supported
ing to integrate petrochemical production to main- SATORP to meet its objectives in two steps: (i) optimal
tain or even increase profitability in
the face of slowing growth in fuel
demand. In this article, we describe
Riser outlet temperature, ˚C
Feed specific gravity, g/ml

Zavanti additive, Grace’s latest

ZSM-5 technology for maximum
propylene FCC applications, and
how the company worked closely
with Saudi Aramco Total Refining
and Petrochemicals (SATORP) to
capture the most value from using
this technology in their operations. Rank Rank

SATORP is one of the world’s most Industry SATORP

efficient integrated refining and pet-

rochemicals platforms. Operational
since 2014, it has one of the most
C4= yield, wt%FF
C3= yield, wt%FF

complex and efficient sites, capa-

ble of converting a type of heavy,
high-sulphur crude oil to high value
added products. To accomplish this,
the refinery relies on a broad range
of processing units, including two Rank Rank
distillate hydrocrackers, an FCC
unit, and a coking unit. In early 2018, Figure 1 Benchmarking plots indicate relative ranking of SATORP’s FCC unit compared
the SATORP platform’s production with other FCC units in the EMEA region in terms of key properties: feed specific gravity,
capacity was raised to 440 000 b/d of riser outlet temperature, and yield of C3= and C4=

www.digitalrefining.com/article/1002648 PTQ Q3 2021 43

 tion, circulation, and performance of
a catalyst in FCC units. When Grace
developed Zavanti additive, it was
Zavanti additive is Grace’s newest additive designed specifically for maximum
2019 propylene FCC units. important to retain the same strong
physical properties (see Table 1) as
2014 OlefinsUltra MZ additive is for very high propylene applications. OlefinsUltra additives.
2010 OlefinsUltra HZ additive is for propylene focused applications.
Activity retention
OlefinsUltra additive is for applications where moderate-to-high propylene The higher severity conditions typ-
2002 production is required. ical of max propylene units pose a
1985- OlefinsPlus, OlefinsExtra and OlefinsMax additives were all developed by challenge to the stability of ZSM-
Grace.
2001
5, in terms of surface area, acid
Additive O was the first ZSM-5 additive developed by Grace Davison in
1984 collaboration with Mobil.
site density, and activity retention.
Therefore during the development
of Zavanti one goal was to show
Figure 2 Grace’s developments in ZSM-5 additive technology high stability or activity retention
with respect to OlefinsUltra addi-
Typical physical properties of Zavanti vs OlefinsUltra additive grades tives. These improvements were
achieved with the use of a new
Zavanti additive OlefinsUltra MZ additive OlefinsUltra HZ additive binder and changes in the processing
ABD, g/cm3 0.72 0.72 0.73 technology. Surface area and activ-
Davison Index (attrition) 5 5 6 ity retention can play a key role in
0-40% 7 7 6
APS µm: 80 78 80
the effective activity of an additive
Surface area, m2/g High High Moderate to maximise propylene yield in the
unit. For two additives having equal
Table 1 starting activity for LPG olefins pro-
duction but different activity reten-
catalyst design to help close the FCC unit’s heat bal- tion with time (half-life decay), the additive with the
ance and achieve improved reliability and utilisation, best activity retention or longer half-life decay will have
yet maximise gasoline olefins; and (ii) optimisation of a higher effective activity in the unit.
ZSM-5 additive to crack gasoline olefins into valua-
ble C3= and C4=s. Optimisation of catalyst design was LPG olefin activity
the subject of a recent presentation.3 In this article we The activity of ZSM-5 additive can be increased either
will focus on the application of Zavanti additive in the by adding more ZSM-5 to a catalyst particle or by
SATORP FCC unit. increasing the inherent activity of the ZSM-5 crys-
tal. Traditionally, adding more ZSM-5 to an additive
Developments in ZSM-5 catalyst technology particle to boost LPG olefin activity was a common
In FCC, the ZSM-5 catalysts are also known as ZSM-5 approach. This has been the case for OlefinsUltra
additives as they are always used in combination with additives. This approach is not trivial since it
FCC catalyst formulated with Y-zeolite. Grace commer- becomes increasingly difficult to bind larger quan-
cialised the first ZSM-5 catalyst, Additive O, in collabo- tities of ZSM-5 in an additive particle and yet retain
ration with Mobil in 1984. Since then the company has good physical properties (particle density and attri-
made advances in formulation and in the technologies tion resistance). This approach has limited potential
used to stabilise and bind the ZSM-5 crystal in catalyst towards increasing LPG olefin activity since it is very
particles. This is shown in Figure 2. difficult to add more zeolite beyond a certain point.
Grace’s R&D programme during Zavanti’s develop-
Zavanti additive ment focused more on increasing the inherent activ-
Zavanti additive has the following features: physical ity of ZSM-5. The objective was to increase propylene
properties required for optimum circulation in the unit, activity by minimal to no increase in the amount of
high retention of ZSM-5 activity, and maximum LPG ZSM-5 in a catalyst particle. This was achieved with
olefin activity. In this section we describe each feature use of a better stabilisation and binding technology.
then present a comparison of activity between the three As Figure 3 shows, the result was a significant increase
most recent generations of ZSM-5 additives from Grace. in propylene activity for Zavanti compared with
Finally, we summarise the results of trialling Zavanti in OlefinsUltra additives.
the SATORP FCC unit and estimate the value delivered.
Laboratory testing
Physical properties To show the difference in activity between Zavanti and
In FCC units, the physical properties of a catalyst are previous generations of ZSM-5 additive technology,
critical for the smooth operation of a unit. Properties Grace tested against OlefinsUltra HZ and OlefinsUltra
such as attrition, apparent bulk density (ABD), surface MZ additives in an Advanced Catalytic Evaluation
area, and particle size distribution are key to the reten- (ACE) unit using a VGO feed.

44 PTQ Q3 2021 www.digitalrefining.com/article/1002648

 250
ACE performance data in wt% delta yields: yield of olefins additives blend minus
Relative propylene activity, %
yield of base FCC catalyst at 75 wt% conversion (5% additive comparison)
200
5 wt% Zavanti in 5 wt% OlefinsUltra 5 wt% OlefinsUltra HZ
150 catalyst blend vs MZ in catalyst blend in catalyst blend vs
base FCC catalyst vs base FCC catalyst base FCC catalyst
Cat-to-oil ratio 0.21 0.31 0.38
100
Hydrogen -0.02 -0.01 -0.01
Ethylene 0.85 0.61 0.39
50 Dry gas 0.55 0.57 0.30

0 Propylene 6.49 5.39 4.30
Propane 0.44 0.39 0.29
a®

HZ

I™
M

NT
tr

a®

a®

Isobutylene 1.50 1.26 1.01

l
sU

VA
tr

tr
fin

ZA
sU

Total C4=s 2.99 2.58 2.06

sU
le

fin

fin
O

Isobutane 0.44 0.45 0.36

le

le
O

Total C4s 3.44 3.07 2.43

LPG wt% 10.31 8.85 7.02
Figure 3 Propylene yield in OlefinsUltra
ZSM-5 additives (previous generation) Gasoline -10.98 -9.45 -7.60
increases with the increased zeolite con- RON 1.57 1.59 1.19
tent of the additive. In Zavanti additive, MON 0.79 0.95 0.69
the increase is due to improvement in the
LCO -0.45 -0.39 -0.12
inherent activity of ZSM-5
Bottoms 0.45 0.39 0.10
For performance testing, the ZSM-5 Coke 0.12 0.03 0.28
catalysts were deactivated separately Table 2
and then blended at two different
levels with the base FCC catalyst con- ACE performance data in wt% delta yields: yields of olefins additives blend minus
taining Y-zeolite. The base catalyst yields of base FCC catalyst at 75 wt% conversion (23% additive comparison)
chosen for this study is a low rare
earth catalyst to minimise hydro- 23 wt% Zavanti in 23 wt% OlefinsUltra 23 wt% OlefinsUltra HZ
gen transfer reactions and maximise catalyst blend vs MZ in catalyst blend vs in catalyst blend vs
base FCC catalyst base FCC catalyst base FCC catalyst
gasoline olefins. The base FCC cata- Cat-to-oil ratio 0.99 0.94 0.95
lyst was deactivated using a milder Hydrogen -0.02 -0.02 -0.01
hydrothermal deactivation protocol Ethylene 2.67 2.04 1.58
of four hours in 100% steam at 1500°F Dry gas 2.49 1.90 1.55

(815°C) whereas a severe deactiva- Propylene 9.23 8.90 8.42
tion protocol was followed for olefins Propane 1.03 0.79 0.69
additives. The olefins additives were Isobutylene 1.88 1.85 1.83
hydrothermally deactivated for 50h Total C4
=s 3.49 3.60 3.61
Isobutane 0.32 0.31 0.47
in 100% steam at 1500°F (815°C) com- Total C4s 3.99 4.01 4.17
pared to the standard deactivation LPG wt% 14.25 13.70 13.28
protocol of 24h.3
For ACE testing, the deactivated Gasoline -16.95 -15.83 -15.36
RON 2.63 2.51 2.55
olefins additives were blended at 5 MON 1.51 1.42 1.52
wt% and 23 wt% level with the base
FCC catalyst. The low blending ratio LCO -0.45 -0.46 -0.36
was used for better differentiation of Bottoms 0.45 0.46 0.36
Coke 0.21 0.22 0.53
two high activity olefins additives
whereas the high blending ratio was
used to evaluate its application for Table 3
max propylene FCC units. ACE data,
at constant conversion, expressed as deltas in wt% yield decrease in gasoline is observed, which is due to crack-
between catalysts with and without olefins additive, are ing of gasoline range olefins to light olefins.
shown in Table 2 and 3, compared at 5% and 23% addi- At higher blend level (23 wt%), Zavanti still
tive blend levels, respectively. shows about 6% higher delta propylene yield over
The data reveal that Zavanti technology produces OlefinsUltra MZ. The advantage of Zavanti is lower
higher propylene yield compared to OlefinsUltra MZ as at high additive level since there is less gasoline range
well as OlefinsUltra HZ at both low and high blending material left to crack and what remains are mostly C5
levels. and C6 olefins which are more difficult to crack. The
At 5 wt% blend in the base catalyst, Zavanti shows a results indicate that greater yields of LPG olefin yields
~20% increase in delta propylene yield over OlefinsUltra can be obtained at constant additive level of Zavanti
MZ. The higher activity of Zavanti is also reflected in versus OlefinsUltra MZ, or similar LPG olefin yields
higher yields of ethylene and butylene. A corresponding can be obtained by using lower percentages of Zavanti

www.digitalrefining.com/article/1002648 PTQ Q3 2021 45

 Raw data and FCC SIM comparison shifts
Reactor product Raw data yield shifts: Zavanti FCC-SIM yield shifts: Zavanti minus
minus OlefinsUltra HZ additive, wt% OlefinsUltra HZ additive, wt%
C2- offgas yield (C2=) +0.20 +0.18
C3= +0.41 +0.65
Total C4=s +0.33 +0.39
Gasoline -0.94 -1.22
Table 4
versus OlefinsUltra MZ. The lower usage of olefins
additive in max propylene FCC units will help to main-
tain the high activity of base catalyst by minimising the
dilution effect. The higher catalyst activity can be lev-
eraged to increase conversion, therefore improving the
profitability of the FCC unit.
The data reveal that Zavanti achieves a higher pro-
pylene yield compared to OlefinsUltra HZ. At 23 wt%
blend, Zavanti shows a ~11% increase in delta propylene
yield over OlefinsUltra HZ, the incumbent ZSM-5 cat-
alyst at SATORP. The data clearly show the ranking in
activity: Zavanti > OlefinsUltra MZ > OlefinsUltra HZ.
The data demonstrate that Zavanti formulated with
Grace’s binding and stabilisation technology delivers a
much higher boost in propylene yield over the incum-
bent additive technology and is the clear choice for the
SATORP unit to maximise propylene yield. Therefore,
Zavanti was preferred over OlefinsUltra MZ for the
SATORP trial.
Summary of SATORP FCC unit data
The performance of Zavanti in the SATORP FCC
unit was assessed by comparing the commercial test
run data during the period of its use against that of
OlefinsUltra HZ, the incumbent ZSM-5 additive. Table
4 summarises the shifts in yields both for the raw data
and the data normalised for operating and feed con-
ditions via FCC-SIM modelling. OlefinsUltra HZ in
inventory was slightly higher than that of the Zavanti
test run. Despite this, as can be seen, the raw data
indicates higher LPG olefin yields with Zavanti vs
OlefinsUltra HZ and the modelling indicates that, once
the test run conditions are normalised, Zavanti outper-
forms further. It is worth noting that in Table 4 the C2-
offgas delta is composed of C2=.
Using the generic price set in Table 5 and the yield
shifts in Table 4, we can estimate the value uplift deliv-
ered by Zavanti additive over OlefinsUltra HZ additive.
In the case of SATORP, the expectation is that the
improvement in C3= and C4= could have been even
higher if the ROT could have been increased. However,
this is not possible at present due to unit constraints.
Assuming typical specific gravity values for various
products, we project uplift of between $0.38/bbl and
$0.58/bbl. Maximising LPG olefins can be highly profita-
ble for a refiner and Zavanti additive technology can be a
tool for refineries with this objective to unlock that value.
Conclusion
Facing the prospect of decreasing fuels demand, refiner-
ies are opting to produce higher yields of petrochemical
46 PTQ Q3 2021
Generic price set for various
refinery products
Product Price, $/t (generic)
C2= 700
C3= 989
Total C4=s 531
Gasoline 483
Table 5
products. The FCC unit, with its high yield of C3=, can
facilitate this transition from fuels to a petrochemicals
focus. The value delivered at SATORP ranged between
$0.38/bbl and $0.58/bbl with Zavanti additive. This
example illustrates the value that petrochemical yields
and new additive technologies can deliver for a refinery.
This article includes contributions from the SATORP FCC team.
ZAVANTI is a mark of W.R. Grace & Co. FCC-SIM is a mark of KBC.
References
1 Large integrated crude-to-chemicals sites in China – the next mega-
trend, Wood Mackenzie, Apr 2018.
2 Crude-to-Chemicals: Opportunity or Threat?, Wood Mackenzie
webinar, Mar 5, 2019.
3 FCC Petrochemical Maximization by Catalyst Selection, Presentation
at BBTC Mena & ME-CAT, SATORP, Dec 2020.
4 Cipriano et al, ZAVANTI™ catalyst: Newest ZSM-5 technology for max
propylene Units, Grace Catalagram, Vol 125, 2020
Silviu Serban is a Technical Sales Manager with Grace Refining Catalyst
Technologies Middle East & Africa. With 18 years’ experience, especially
in FCC and other refinery units, he previously worked on the SATORP
refinery project in Saudi Arabia, as a Production Engineer for Amromco
Energy in Romania and in the US, and at the S.C. Petrotel – Lukoil refinery
in Romania. He holds a MSc degree from the “Oil and Gas” University of
Ploiesti, Romania.
Chuck Ekeocha is Technical Service Manager with Grace FCC, Middle East
& Africa. With 14 years’ experience, he has worked in refining operations,
design and project management with a focus on catalytic reforming, fluid
catalytic cracking, hydrotreating, crude distillation, sulphur recovery, and
refinery utilities. He holds BSc & MSc degrees in chemical engineering
from the University of Science and Technology, Ghana and the University
of Newcastle-upon-Tyne, UK, and is a member of the Institute of
Chemical Engineers.
Udayshankar Singh is Senior Principal Research and Development
Scientist in the Refining Technologies business with W.R. Grace &
Co.-Conn., Columbia, Maryland. He has 14 years’ experience in the
development and scale-up of new catalysts for various FCC applications
and provides technical support to customers. He holds a PhD in chemistry
from The Open University, UK, spent two years as a postdoctoral research
fellow at the University of Exeter, UK, three years as a postdoctoral
research fellow at the University of California-Santa Barbara, and is an
inventor of several patents.
Bani H Cipriano is FCC Segment Marketing Manager, Light Olefins
with W.R. Grace & Co and manages the company’s portfolio of max
propylene catalysts and ZSM-5 additives. His priority is to commercialise
technologies that will enable customers to maximise yields of
petrochemical feedstocks from the FCC unit. He holds BS and PhD
degrees in chemical engineering from the University of Maryland.
LINKS
More articles from: W. R. Grace &Co
More articles from the following categories:
Catalysts and Additives
Fluid Catalytic Cracking
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