Selective FCC naphtha
desulphurisation
By combining specially designed catalyst and process technology, the SCANfining
process selectively removes sulphur from FCC naphthas while preserving olefins
K L Riley, J L Kaufman and S Zaczepinski Exxon
A R Gentry Kellogg Brown & Root Inc P H Desai Akzo Nobel Chemicals Inc
B
eginning in 1995, the US Environmental
Protection Agency (EPA) required gasoline
sold in areas with below-standard air qual-
ity to meet certain reformulated gasoline (RFG)
standards. Initially, the sulphur content of gaso-
line was tied to historic company levels. On 1
January 1998 the baseline sulphur content was
changed to an historical industry average and
gasoline emissions of RFG were defined by a
Phase 1 complex-model. This resulted in many
refiners making modest reductions in gasoline
sulphur levels.
When the Phase 2 complex-model RFG perfor-
mance standards are introduced on 1 January
2000, many refiners will probably reduce
sulphur levels again in order to comply.
Recent gasoline quality proposals for the
European Union for the years 2000 and 2005
require significant reductions in sulphur level. In
the Asia Pacific region Japan already has a
low-level specification. It is anticipated that
Canada will follow the US lead in higher quality
gasoline, most likely with lower sulphur levels.
Sulphur in gasoline comes mainly from three
refinery streams: FCC naphtha, coker naphtha
and straight-run naphtha. Of these streams the
FCC naphtha is the largest contributor, being
responsible for 40–90 per cent of the sulphur in
the final product. To achieve lower sulphur
levels, the refiner must produce lower-sulphur
FCC naphtha.
Although refiners have a number of process
options for reducing the sulphur level in FCC
naphtha, two that are generating the most inter-
est are: hydrotreating the feed to the FCC unit
and hydrotreating the FCC naphtha.
www.digitalrefining.com/article/1000684
Hydrotreating the FCC feed improves naphtha
yield and quality and reduces the SOx emissions
from the FCC unit, but it is typically a high-pres-
sure process and is therefore very
capital-intensive. Furthermore, manipulation of
process feed sulphur alone may not be sufficient
to meet future gasoline performance standards.
Refineries wishing to process heavier, less
expensive crudes will be forced to desulphurise
the resulting higher-sulphur naphthas.
Hydrodesulphurisation of FCC naphtha is a
low-pressure process and is therefore not as
capital-intensive as FCC feed hydrotreating. The
selection of an optimum hydrotreating process
option for reducing sulphur in FCC naphtha is
determined by economic factors specific to a
refinery.
In response to a reformulated gasoline and
high-sulphur crudes environment, Exxon
Research & Engineering Co. (ER&E) has devel-
oped the SCANfining (proprietary process name
of ER&E) process. This process uses the RT-225
catalyst jointly developed and commercialised
with Akzo Nobel, and a combination of process
design and operating conditions that maximise
catalyst performance.
The RT-225 catalyst is specially designed to
selectively remove sulphur from FCC naphthas
while preserving olefins in order to avoid unde-
sirable octane loss and higher H2 consumption.
This combined catalyst/ process technology
package is suitable for retrofit and grassroots
units and is now available for license. The
process was commercialised in 1994.
SCANfining is marketed by both ER&E and
Kellogg Brown & Root (KBR).
PTQ Q2 1999 1

RFG standards to be met by US refiners
Most
Year 1995 1998 2000
Phase 1 1 1 sensitive
Model Simple Complex Complex gasoline
parameter
Emission: % Reduction
NOx – 1.52 6.82 Sulphur
VOC ~16 17.12,3 27.42,3 RVP
Toxics 16.51 16.52 21.52 Benzene The difficult tradeoffs that the refiner will have
1 1990 Company Baseline,
2 1990 Industry Baseline,
3 Region 2 (North)
Table 1
Background
The EPA introduced reformulated gasoline
standards in the U.S. to help certain areas meet
the National Ambient Air Quality Standards for
atmospheric ozone concentrations. These stand-
ards require a reduction in NOx, volatile organic
compounds (VOC), and other compound emis-
sions according to a phased-in schedule. Table 1
summarises the emission reductions scheduled
for the USA along with the most sensitive gaso-
line parameters that affect these emissions.
In 1995, the EPA required gasoline sold in
non-compliance areas to satisfy RFG standards
defined by the simple model which included just
a few variables such as oxygen and benzene
contents, and Reid Vapour Pressure (RVP). This
simple model controlled VOC emissions by limit-
ing summer regional RVP, required a reduction
of other regulated compound emissions by a
minimum of about 16 per cent relative to 1990
baseline values, and ensured that NOx levels
would not increase.
In these regulations, sulphur, olefins, and T90
(90 per cent boiling point) in gasoline were
limited to the 1990 company levels [Rhodes A K,
Oil & Gas Journal, 17 January 1994]. Beginning 1
January 1998, the quality of RFG was defined
for the first time by a complex model that calcu-
lates emissions, using eight gasoline quality
parameters, including sulphur, benzene, aromat-
ics, and olefin concentrations, RVP, and
evaporative properties.
In order to comply with the regulations and
meet emission limits, a refiner’s gasoline proper-
ties must fall within accepted ranges for all eight
parameters.
The structure of the complex model indicates
2 PTQ Q2 1999
that the gasoline parameters that most affect
NOx emissions are sulphur, RVP, aromatics, and
olefins. After considering the nature of the
complex model, it appears that reducing sulphur
will be the primary means refiners will use to
comply with the NOx reduction standards sched-
uled for 1998 and 2000 [Rhodes A K, Oil & Gas
Journal, 5 January 1998].
to make in adjusting gasoline parameters are
illustrated by olefin saturation. Although reduc-
ing olefins leads to decreasing NOx emissions, it
also increases VOC emissions. Since the complex
model indicates that reducing sulphur in gaso-
line has the largest impact on reducing NOx
emissions, this process objective has become
very important to the US refiner.
Other regions of the world are also aggres-
sively moving to reduce NOx emissions by
limiting the sulphur level in gasoline. For gaso-
line-fuelled cars, a 1996 European Union
directive reduced the allowable hydrocarbon and
NOx emissions for new cars by nearly 50 per
cent. In 1998, the European Parliament issued
specifications for gasoline that include a sulphur
limit of 150ppm by the year 2000 and 50ppm by
2005 [Hart’s European Fuels News, 1 July 1998].
In the USA, the Environmental Protection
Agency is considering reducing gasoline sulphur
levels. In Japan, the current gasoline specifica-
tion for sulphur is 100ppm, with the possibility
of more severe specifications in the future.
Process options
Conventional cat naphtha hydrotreating technol-
ogy is based on catalytic reforming feed
preparation utilising relatively high pressure to
desulphurise product to less than 1ppm sulphur
with virtually no olefins remaining. Although a
50ppm sulphur level in the gasoline pool could
be achieved by this approach, it would probably
require hydrotreating the entire FCC naphtha
fraction.
This would lead to a substantial octane loss
because of olefin saturation (OS) in the light-gas-
oline fraction. A 7–10 loss in research octane
number (RON) and a 3–4 loss in motor octane
number (MON) could be expected [Rhodes A K,
Oil & Gas Journal, 17 January 1994].
Hydrotreating only the intermediate and heavy
fractions of the FCC gasoline is a process option
that minimises the octane loss associated with
www.digitalrefining.com/article/1000684
hydrodesulphurisation. Since the
sulphur compounds are typically
concentrated in the heavier frac-
tions, and the high octane olefins
are found mainly in the light and
intermediate fractions, hydro-
treating the heavier fractions
results in a significant decrease
in sulphur content and a lower
octane loss.
This is especially true if the
intermediate boiling fraction,
which contains high concentra-
tions of both sulphur and olefins,
is processed with HDS technol-
ogy that selectively removes
sulphur while preserving olefins Figure 1 Cases representing FCC naphtha hydrotreating operations
to avoid octane loss.
To achieve the maximum savings in octane selective. The hydrotreated SCANfining products
and H2 consumption, both process conditions typically show the smallest bromine number
and a catalyst that selectivity favours hydrodes- delta for a given percentage HDS among the
ulphurisation (HDS) reactions over OS reactions array of third party technologies currently avail-
must be used. To illustrate the possible olefin able. By comparing investment, Doctane, C5+
savings, Figure 1 shows operating curves formed yield, and H2 consumption, the selective
by varying process conditions for three cases: A, SCANfining catalyst and process technology is
the most selective catalyst and process condi- an attractive FCC naphtha HDS option for the
tions; B, a less selective catalyst than Case A; refiner.
and C, a non-selective catalyst and process
conditions representing conventional operations. RT-225 development
By comparing at a target HDS level of 90 per RT-225 was developed and commercialised in
cent, Figure 1 shows that Case A has the lowest 1994 for use in a heavy cat naphtha (HCN)
amount of olefin saturation (most selective), hydrotreating unit in a North American refinery.
followed by Case B and then Case C. Case C Its development and commercialisation required
shows that a substantial amount of olefin satura- a broad team effort between personnel from
tion can occur by using non-selective catalyst ER&E’s Engineering Group, the Exxon Research
and operating conditions. The figure further & Development Laboratories (ERDL), the refin-
shows that if the target HDS level was 99 per ery, and Akzo Nobel. Through intensive effort,
cent-plus, olefin saturation may reach 70 per the team achieved the commercialisation in only
cent-plus, even for the most selective Case A, six months. This represented the period from
resulting in greater octane loss and H2 the date that the refinery identified the incen-
consumption. tives for using RT-225 to the date the catalyst
The SCANfining process using the RT-225 was delivered to the refinery to load into the
catalyst is specially designed to achieve high reactor.
HDS/OS selectivity with excellent HDS activity This success was accomplished despite the fact
maintenance. Because of the importance of the that a new metals impregnation procedure had
support-metals interaction and the support to be developed for plant use. Figure 2 shows an
design features, catalyst preparation procedures historical timeline for the RT-225
developed with Akzo Nobel are a key feature of commercialisation.
the RT-225 technology package. In early May 1994 the refinery requested that
In third party technology comparisons, the ERDL participate with the Engineering Group in
SCANfining process for selectively desulphuris- a study comparing several commercially availa-
ing FCC naphtha was found to be the most ble catalysts with the design basis catalyst for

www.digitalrefining.com/article/1000684 PTQ Q2 1999 3

 particles could not be
obtained using commercial
manufacturing plant opera-
tions. A new procedure would
have to be developed.
Rather than give up, due to
the tight time schedule for
supplying the catalyst, refin-
ery personnel encouraged
continued efforts to prepare
the new catalyst. Akzo Nobel
and ERDL intensified their
efforts and a new procedure
was demonstrated by
Figure 2 RT-225 development and commersialisation, 1994–1995 mid-November. The catalyst
was produced and certified in
December and the refinery
unit started up in early
February 1995.
The catalyst has proven to
be robust in commercial
service. Over the unit cycle
length, operations have
covered a wide range of
conditions and feeds. The
range of feed quality to the
unit is summarised below:

Specific gravity 0.825–0.845

Sulphur, wppm 800–3000
Bromine No., cg/g 14.5–34.5
GC 10%, °C (°F) 88-121 (190-250)
GC 95%, °C (°F) 216-238 (420-460)

Figure 3 SCANfining selectivity in commercial operations The unit has demonstrated

their new HCN hydrotreater. Since ERDL’s
exploratory research group had just discovered a
new, selective HDS catalyst that was appropriate
for this application, the new catalyst lead was
included in the evaluation.
In the first week of July, ERDL presented its
findings to the refinery and recommended using
the new RT-225 catalyst. Shortly after the refin-
ery accepted this recommendation, ERDL
contacted Akzo Nobel about commercially
preparing the catalyst. It was during the early
Akzo Nobel laboratory scale-up work in October
that problems were identified in the preparation
procedure.
Using an impregnation procedure derived
from the ERDL exploratory work, it was discov-
ered that a uniform metals profile in the catalyst
the selectivity that is achieva-
ble with the SCANfining process. Figure 3 shows
the level of olefin saturation observed at a given
desulphurisation level during the entire operat-
ing cycle.
The ability of RT-225 to maintain HDS/OS
selectivity is shown in Figure 4. In this chart the
selectivity, defined as the ratio of HDS activity to
OS activity, is shown during an extended period
of the commercial run.
Conclusion
Future worldwide environmental regulations
designed to reduce NOx, volatile organic
compounds and other regulated compound
emissions from automobiles will put pressure on
refiners worldwide to significantly reduce the
sulphur level in FCC naphthas. Although refiners

4 PTQ Q2 1999 www.digitalrefining.com/article/1000684

have various process
options for achieving this
objective, selective hydro-
treating of the intermediate
cat naphtha (ICN) and/or
the heavy cat naphtha frac-
tions can be economically
attractive because of lower
capital investment require-
ments and lower operating
costs from limiting product
octane losses and H2
consumption.
To achieve the maximum
savings in octane and H2
consumption, it is important Figure 4 SCANfining selectivity maintenance
to use both a catalyst and
process conditions that favour hydrodesulphuri- processes engineering, refinery operations management and
sation reactions over olefin saturation reactions. R&D management for more than 30 years.
Exxon Research & Engineering has developed Arthur R Gentry is technical director, hydroprocessing, for Kellogg
and commercialised the SCANfining process for Brown & Root Inc, Houston, Texas, with over 28 years’ experience
in process design, development and management of refining
achieving selective FCC naphtha desulphurisa-
technologies.
tion. By using the proprietary RT-225 catalyst Pankaj H Desai is the development manager for Akzo Nobel
with the appropriate process conditions, high Chemicals Inc at Houston, and since joining the company in 1980
HDS/OS selectivity can be maintained over has worked in the areas of hydroprocessing and FCC catalysts.
extended cycle lengths for both retrofit and
grassroots applications.

Kenneth L Riley is with Exxon Research and & Development LINKS

Laboratories, Baton Rouge, Louisiana, USA, and has 31 years’
experience in catalyst and process development. More articles from: KBC Advanced Technologies
Jeffrey L Kaufman is a hydroprocessing specialist with Exxon
More articles from the following categories:
Research and Engineering Co, at Baytown, Texas, with over 25
Desulphurisation & Sulphur Handling
years’ experience in operations and process engineering.
Fluid Catalytic Cracking
Sam Zaczepinski is licensing manager for Exxon Research
and Engineering. Florham Park, New Jersey, and has been in

www.digitalrefining.com/article/1000684 PTQ Q2 1999 5