Special Focus Process Optimization

B. AGGUS, INVISTA Performance Technologies,

Corpus Christi, Texas; and M. MASSA, INVISTA Performance
Technologies, Nashville, Tennessee

Octane upgrading technology to boost value

of light paraffinic feeds
In November 2017, US crude oil production eclipsed the potential for catalyst damage due to inadvertent introduction of
10-MMbpd mark, setting the highest production record in wet feed. The key to this technology is the proprietary catalyst
history. The 2017 growth in production was primarily driven and the associated chemistry.
by the Permian basin, situated in West Texas and Southeast
New Mexico. Permian producers added 460,000 bpd between Catalyst and chemistry. The catalyst is a complex-metal-
2016 and 2017. Year-over-year US onshore production grew modified, nano-size ZSM-5 type. It provides an immediate
1.4 MMbpd from December 2016 to December 2017, and as octane boost by isomerizing alkanes, which subsequently can
a result of the increase in production from these onshore tight also crack, oligomerize and aromatize to form additional high-
oil basins, the US crude slate is becoming increasingly lighter.1 octane, value-added compounds. While zeolites are commonly
This trend is expected to continue, creating an excess of light used as catalysts and adsorbents in refining, the marriage of dis-
paraffinic naphtha destined for export as cracker feed, since the persed metals, tailored acidity and customized carrier structure
gasoline pool is unable to absorb these low-octane, high-Reid- makes this catalyst unique. The catalyst structure is orchestrat-
vapor-pressure (RVP) materials. ed to deliver the optimum crystal size, cell size, carrier porosity,
pore distribution and metal crystallite distribution to facilitate
Octane upgrading vs. isomerization. Targeting this mar- access to the active sites (FIG. 2).
ket need, a commercially proven octane upgrading technologya The catalyst metals play a critical role in the alkane activa-
isomerizes and aromatizes C5 through C7+ paraffinic streams, tion, isomerization and dehydroaromatization chemistry. The
such as straight-run naphtha, topped oil, raffinate oil, Fischer- catalytic process is initiated with the isomerization and subse-
Tropsch naphtha and/or natural gasoline. This innovative tech- quent cracking of alkanes, which is facilitated by the uniquely
nology simultaneously raises the octane, lowers the RVP and tailored acid functionality of the zeolite. This cracking process
reduces sulfur content by approximately 90%. It utilizes stan- creates branched carbocations that can either recombine to
dard refining equipment and unit operations, such as fixed-bed form higher-molecular-weight branched species of higher oc-
reactors, absorption and fractionating columns, shell-and-tube tane value, or undergo β-scission to form olefin components.
exchangers, etc. The robust catalyst system is tolerant to impuri- The olefinic compounds predominantly undergo dehydroaro-
ties that can be catastrophic to alternate technologies that pro- matization, forming three moles of hydrogen per mole of aro-
cess these feeds (FIG. 1).
Isomerization, which requires complex feed preparation and
treatment, is the primary alternative for these types of feeds. The
isomerization process isomerizes a C5/C6 feed stream, boosting
octane by converting the n-paraffins to iso-paraffins. The pro-
cess cannot tolerate sulfur in the feed and, therefore, requires a
hydrotreater with makeup hydrogen and associated compres-
sion. The feed must be tightly fractionated to minimize C7 mate-
rials in the feed, which will coke the catalyst. In addition, the feed
must be dry to prevent catalyst deactivation due to the presence
of water. An isomerization process with recycle has advantaged
yields at the price of significantly higher CAPEX and OPEX.
In contrast, octane upgrading technology requires no pre-
treatment to remove sulfur, provided the sulfur in the feed is less
than 200 ppmwt. This eliminates the CAPEX and OPEX asso-
ciated with naphtha hydrotreating. In addition, hydrogen is not
required in the process, so sourcing and handling of hydrogen
FIG. 1. An operating plant in 2013.
are eliminated. The catalyst is water tolerant, eliminating the
Hydrocarbon Processing | JANUARY 2019 37
 Process Optimization
matic ring. The catalyst favors formation of toluene, xylenes and
C9 aromatics with low benzene formation.
The unique metal combination and deposition provides cat-
alyst stability, with long run lengths of up to 60 d between cata-
lyst regeneration cycle times in commercial operation. Coking
is the primary deactivation mechanism of the catalyst, requiring
periodic oxidative regeneration to restore activity. The typical
catalyst regeneration cycle is 7 d–10 d, and the overall catalyst
life is longer than 2 yr.
Process description. Two or more reactors are operated in
parallel, with the feed equally distributed among the reactors
during normal operation. When one reactor is being regener-
ated, 100% of the feed is processed through the remaining
reactor(s) (FIG. 3).
The feed to the reactor is first processed through a series of
heat recovery exchangers, followed by a fired heater to achieve
the desired inlet temperature, typically 570°F–790°F (300°C–
420°C). The overall reaction is endothermic. However, olefin-
containing liquefied petroleum gas (LPG) can be co-fed to the
FIG. 2. The catalyst structure is orchestrated to deliver the optimum
specifications to facilitate access to the active sites.
Dry gas
Dry gas
Catalyst
reactor Stabilizer LPG
Stabilizer
Not required if
Gasoline product
light naphtha
feed only
Light naphtha feed
LPG co-feed
FIG. 3. Process flow diagram showing two or more reactors operated
in parallel, with the feed equally distributed among the reactors
during normal operation.
38 JANUARY 2019 | HydrocarbonProcessing.com
reactor in proportion to the naphtha feed to minimize heat in-
put. Oligomerization of the olefins in the LPG feed is a highly
exothermic reaction. This co-fed LPG increases yields, reduces
energy consumption and improves the octane of the final prod-
uct by three to five points.
The reactor is a fixed-bed reactor with typically three to five
beds per reactor, depending on the throughput. The catalyst
gradually cokes during operation, and the feed temperature is
correspondingly increased to maintain the desired yield and
octane. As the temperature reaches the 790°F–840°F (420°C–
450°C) range, the rate of coking increases and the reactor is
taken offline for regeneration.
Product leaving the reactor is passed through feed/product
heat exchangers, where it is partially condensed. This stream is
passed through the stabilizer feed drum, in which the liquid and
gas products are separated, with both streams being fed forward
to the stabilizer column. The stabilizer reboiler duty is adjusted
to optimize the RVP of the gasoline blendstock.
If LPG is co-fed to the process, then a second column can
be added to facilitate better separation of the offgas (C1, C2 and
H2 ), LPG and gasoline products.
Recommendation. If a refinery is getting the economic short
end of long naphtha, the octane upgrading technology de-
scribed in this article can generate higher value from light paraf-
finic streams destined for export.
This low-CAPEX, operator-friendly process converts low-val-
ue paraffinic streams into high-value gasoline blendstock. Actual
yields and octane enhancement depend on the feed composition
and the final product octane target. The six units in operation
and three units under construction are designed for a variety of
feeds. Typical yield is approximately 70 wt% C5–85 wt% C5. The
octane enhancement increases as the feed octane decreases.
With a primarily C6 /C7 feed, the octane enhancement can
exceed 20 points. The degree of RVP improvement is depen-
dent on the feed composition. Benzene generation is less than
0.7 wt%, and product sulfur content is less than 10% of the feed
content. The catalyst is tolerant of sulfur and water. The pro-
cess utilizes standard refining equipment and has a wide op-
erating window, which is an ideal combination for capturing
return on investment.
NOTE
a
IsoA™ Technology is offered by Koch Industries affiliates INVISTA Performance
Technologies and Koch-Glitsch.
LITERATURE CITED
1
US Energy Information Administration, “This week in petroleum,” March 14, 2018.
BRANT AGGUS is the Senior Refining Technologist for INVISTA
Performance Technologies (IPT) and has worked in the refining
space since 2000 as a process engineer in engineering design,
operations engineering and consulting. He started working
for Koch Industries’ Flint Hills Resources Corpus Christi
Refining Complex in 2012 and recently joined INVISTA,
a Koch Company, in support of refining technology licensing
and business development.
MIKE MASSA is the Licensing Director for INVISTA Performance
Technologies. He worked in operations management roles
in petrochemicals process engineering and research and
development before joining licensing in 1997. Mr. Massa
holds a degree in chemistry and chemical engineering.