Processing Tight Oils in FCC: Issues, Opportunities and

Flexible Catalytic Solutions

Kenneth Bryden, Manager FCC Evaluations Research

Michael Federspiel, National Sales Leader, Americas
E. Thomas Habib, Jr., Director Customer Research Partnerships and DCR Licensing Manager
Rosann Schiller, Marketing Director, FCC Commercial Strategy

Grace Catalysts Technologies

W.R. Grace & Co.-Conn.
7500 Grace Drive
Columbia, MD 21044

Abstract
Tight oils (also called shale oils) such as Eagle Ford and Bakken are fast becoming a major
feed source for North American refineries. While these feedstocks are generally light and
sweet, issues that refiners can face when processing tight oil include: contaminant metals, heat
balance effects, and configurational imbalances in the refinery. This paper provides detailed
characterization of tight oils along with data on the cracking of these feedstocks under different
operating conditions. Catalytic solutions for (1) metals tolerance, (2) achieving maximum
conversion and selectivity on light feeds, and (3) optimum butylene selectivity are discussed
along with case studies on how refiners can apply new catalyst technologies to maximize the
value present in tight oil feedstocks.

1.0 Introduction
As novel technology for hydraulic fracturing with directional drilling continues to develop, tight oil
(also called shale oil) will continue to be a game changer for North American refiners. Although
credited with many advantages, tight oil does not come without its challenges. Suppliers and
processors alike are urgently working to adapt to the changing oil landscape. Just a few years
ago, investments were focused on processing heavy crudes. Now, however, the industry is
faced with lighter, sweeter crude streams from tight oil plays.

In varying degrees at each refinery, tight oil makes up only a percentage of the total feedstock.
In December 2013, production from the Bakken region passed 1.0 MM bbl/day and production
from the Eagle Ford region reached an estimated 1.23 MM bbl/day [1]. The December 2013
production of these two tight oil regions is slightly more than 10% of the total US crude oil
demand. The percentage of tight oil could grow substantially as tight oil production increases
and refiners invest in process modifications to handle this lighter feed. While drilling technology

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advances and the rapid growth of tight oil production have made forecasts difficult, the U.S.
Energy Information Administration currently forecasts that United States tight oil production will
top 4.8 MM bbl/day in 2021 [2]. Tight oil resources are not confined to the United States.
Recent analysis indicates that tight oil formations are located throughout the world and
constitute a substantial share of overall technically recoverable global oil resources [3]. The
January 2014 BP Energy Outlook projects that by 2035 tight oils will constitute 7% of the total
global oil supply, with more than one third of tight oil production coming from outside the United
States [4]. While the North American refining industry undergoes a renaissance due to
abundant tight oil, the new feeds present challenges as well as opportunities. This paper
discusses the challenges with tight oil feeds and how to overcome them with proper choice of
catalyst technology.

2.0 Tight Oil Properties

Tight oil is highly variable. Density and other properties can show wide variation, even within
the same field [5-8]. Tight oils are generally light, paraffinic and sweet. Table 1 presents the
properties of a sample of whole Bakken crude, compared to publically published assays of
Bakken, West Texas Intermediate (WTI) and Light Louisiana Sweet (LLS) and a “typical” Eagle
Ford crude based on the Eagle Ford Marker. Eagle Ford crude is highly variable and the Eagle
Ford Marker is based on a pool of Eagle Ford assays [10]. The Bakken crude is light and sweet
with an API gravity of 42°and a sulfur content of 0.19 wt%. Similarly, Eagle Ford is a light sweet
feed, with a sulfur content of ~0.1 wt% and with published API gravities between 40° API and
62° API, with a value of 47° used for the Eagle Ford Marker. Similar to other light crudes, raw
Bakken crude and Eagle Ford crude have a low amount of FCC feed (<28% 680°F+ for Bakken,
and <27% 680°F+ for Eagle Ford Marker). The straight run Bakken sample was distilled into a
430°F minus gasoline cut and a 430°F to 650°F LCO cut and the properties of these cuts were
measured to better characterize the Bakken feed. The gasoline composition and properties
were analyzed via Grace’s proprietary G-Con® octane calculation software based on detailed
GC analysis [12, 13]. The gasoline fraction from the straight Bakken was highly paraffinic and
had low octane numbers (a RON of 61 and MON of 58). The LCO fraction had an aniline point
of 156°F and an API gravity of 37.6, resulting in a diesel index of 59.

Table 2 presents properties of a 430°F+ distillation of Bakken, a 650°F+ distillation of Bakken,

along with two Eagle Ford based fluid catalytic cracking (FCC) feeds. A typical mid-continent
VGO is included for comparison. The tight oil derived feeds are all light and paraffinic. Table 3
shows the results of an HRMS 22-Component Hydrocarbon Types Analysis of the FCC feeds.
This breakdown of hydrocarbon types further highlights that the Bakken and Eagle Ford crudes
are high in saturates. However, the 650°F+ distillation of the Bakken crude does contain a
significant portion of tetra-aromatics that are inactive to cracking and are coke precursors.

While most tight oils are low in nickel and vanadium, they have been found to be high in
inorganic solids, iron, and alkali metals [6, 14]. Table 4 presents metals analyses of several
tight oil-derived feed streams along with published metals analyses of tight oil. While metals
levels in the samples vary (as would be expected for tight oil), iron and calcium levels are
generally high. Reports from the field indicate that Bakken crude is typically low in nickel and

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vanadium, while crudes sourced from the Eagle Ford formation have higher nickel and
vanadium levels that can vary significantly based on their source.

To better understand the possible sources of metals in tight oil, a sample of whole Bakken crude
was filtered through an 0.8 micron filter and the solids recovered. Scanning electron
microscopy of the solids identified irregular micron and submicron sized particles as shown in
Figure 1. Energy dispersive spectroscopy maps of iron, sulfur and calcium are pictured in
Figure 2. The iron in the sediments is associated with the sulfur.

X-ray diffraction of the sediment identified the following crystalline phases: anhydrite (Ca2SO4),
magnetite (Fe3O4), and pyrrhotite (substoichiometric FeS). Anhydrite and pyrrhotite have been
mentioned in the literature as being present in the Bakken formation [15, 16.] Based on this
analysis, it appears that much of the iron in the Bakken crude comes from very small particles of
iron oxide and pyrrhotite.

3.0 Cracking Yields of Whole Tight Oil and Tight Oil Cuts
To examine the impact of tight oil on FCC yields, cracking was done with whole Bakken, a
430°F+ distillation of Bakken, a 650°F+ distillation of Bakken, two Eagle Ford derived FCC
feeds, and a reference sample of a typical mid-continent VGO. Feed properties are presented
in Tables 1 and 2. Cracking was done over an FCC catalyst in a fixed-fluidized bed ACE test
unit [17] at a constant reactor temperature of 980°F, using three catalyst-to-oil ratios (4,6,8) for
each of the feeds. The catalyst used in the experiments was an FCC catalyst with optimized
matrix and mesoporosity, deactivated metals free using a CPS type protocol. The properties of
the deactivated catalyst are given in Table 5.

Interpolated yields at a catalyst-to-oil (C/O) ratio of 6 are presented in Table 6. The whole
Bakken crude resulted in low coke, and a low octane gasoline. While the whole Bakken crude
yielded significant gasoline, much of the gasoline was from uncracked starting material in the
feed. The yields of the 430°F+ and 650°F+ distillations of the Bakken crude were similar to
those of the mid-continent VGO reference sample. The 650°F+ distillation of the whole Bakken
crude had higher coke than the mid-continent VGO due to its heavier end as seen in its higher
Conradson carbon number and higher tetra-aromatic content. Compared to the mid-continent
VGO, the light Eagle Ford derived feeds yielded higher gasoline and lower coke, bottoms and
LCO.

4.0 Processing Straight Run Tight Oil - Effect of Operating Variables on Yields and
Product Properties
While fluid catalytic cracking is typically done to reduce the molecular weight of the heavy
fractions of crude oil (such as vacuum gas oil and atmospheric tower bottoms), in some cases
refiners are charging whole tight oil as a fraction of their FCC feed. Since tight oil is low in
components boiling above 650°F and high in components boiling below 650°F, a refiner
processing 100% tight oil can be at their maximum distillation and light cut capacity and be short
on FCC feed. Also, whole crude oil has been charged to FCC units when gas oil feed is not

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available due to maintenance on other units in the refinery [18], and to produce a low-sulfur
synthetic crude [19].

As a model case to understand the cracking of whole crude oil in the FCC and the effect of
process conditions on yields, the whole Bakken crude described in Table 1 was processed in a
DCR™ circulating riser FCC pilot plant at three riser outlet temperatures: 970°F, 935°F, and
900°F. As a reference case, the mid-continent VGO described in Table 2 was cracked at a riser
outlet temperature of 970°F. Details of the DCR™ circulating riser pilot plant can be found in
Reference 20. The catalyst used in the experiments was a high-matrix FCC catalyst,
deactivated metals free using a CPS type protocol. The properties of the deactivated catalyst
are given in Table 5.

Figure 3 presents the yield structure of the starting feeds and the cracked products for a riser
outlet temperature of 970°F. The mid-continent VGO is a typical VGO feed with a large portion
of 650°F+ material and small fraction of LCO range material. When cracked, the LCO range
material cracks to LPG and gasoline, and the 650°F+ material cracks to the typical distribution
of LPG, gasoline and LCO, resulting in a net increase in LCO. The whole Bakken crude starts
with large fractions of gasoline and LCO range material and a low amount of 650°F+ material.
The amount of gasoline produced after cracking is high since the LCO range material cracks to
predominantly gasoline and much of the starting gasoline is unconverted. LCO yields are low
since there is little starting 650°F+ material to crack to LCO.

For the three different reactor outlet temperatures, plots of catalyst to oil ratio, gasoline, LCO,
and coke yields versus conversion are shown in Figure 4. As expected, lowering reactor
temperature increases the amount of LCO produced. Cracking straight run tight oil produces
little coke and bottoms. At the same conversion level, lowering reactor temperature results in
slightly more gasoline yield (due to increased C/O), which is consistent with prior work [21]. At a
riser outlet temperature of 970°F, the whole Bakken feed produces more gasoline, less LCO
and less coke than the reference mid-continent VGO. Figure 5 presents plots of gasoline
olefins, iso-paraffins and RON and MON estimated via G-Con®. Cracking straight run Bakken
tight oil produces a paraffinic low-quality gasoline with research octane less than 80 and motor
octane less than 70. At constant conversion, increasing reactor temperature results in more
gasoline olefins and higher research octane number.

Diesel quality is of great interest to refiners. Synthetic crude produced in the circulating riser
pilot plant runs was distilled to recover the 430°F to 650°F LCO fraction. Aniline point and API
gravity of the LCO were then measured to allow calculation of the diesel index, a measure of
LCO quality [diesel index = (aniline point x API Gravity) / 100 ]. Figure 6 presents data for LCO
yield and LCO quality as a function of conversion. As seen in the data, increasing conversion
lowers LCO quality as a result of increased cracking of the LCO range paraffins to lighter
hydrocarbons. As seen in prior work [22], LCO quality follows LCO yield and did not appear to
be influenced by reactor temperature at constant conversion. Diesel index values of the LCO
produced by cracking whole tight oil were significantly higher than those obtained when cracking
the reference mid-continent VGO. At a conversion of 78 wt%, the whole Bakken gave a LCO

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with a diesel index of 40, compared to a diesel index of 10 obtained for the LCO produced from
the mid-continent VGO.

This study of the effect of operating variables shows that whole shale oil responds to FCC
operating conditions similarly to conventional oils. However, the product yield slate is
substantially different in that good quality (high diesel index) LCO is produced in the FCC and
large amounts of low octane gasoline are made.

5.0 Processing Challenges

Light sweet crudes are generally easy to process, although challenges arise when these crudes
are the predominant feedstock in refineries designed for heavier crudes. Tight oils, like other
light sweet crudes, have a much higher ratio of 650°F- to 650°F+ material when compared to
conventional crudes. Bakken tight oil has a nearly 2:1 ratio, while typical crudes such as
Arabian Light, have ratios near 1:1. A refinery running high percentages of tight oil could
become overloaded with light cuts, including reformer feed and isomerization feed, while at the
same time short on feed for the fluid catalytic cracking unit (FCCU) and the coker. Many refiners
report that while they are benefitting from favorable crude prices they often are struggling to
keep downstream process units full. At low FCC utilization rates, oftentimes the alkylation unit
is unconstrained, leading to an octane shortage.

Unconstrained downstream units are just one of the challenges faced by North American
refiners. Unconventional oils can vary wildly in composition from cargo to cargo. Receiving
crude in batches via rail, truck or barge can result in FCC feed changing rapidly over the course
of several weeks or several days. To increase utilization rates, heavier crudes may be blended
with lighter tight oils, resulting in a “barbell” crude, which has a lot of material boiling at each end
of the boiling point curve, but little in the middle, reducing VGO yield for the FCC. As previously
discussed, some refiners have tried charging whole crude to the FCCU in order to boost
utilizations, to the detriment of other key yields such as FCC naphtha octane.

At the FCCU, the challenges range from difficulty maintaining heat balance when the feed is
very light to unexpected coke make when contaminant metals rise rapidly. When operating with
highly paraffinic light tight oil feeds that crack easily and produce little coke, the FCC may
become circulation constrained due to low regenerator temperatures. Refiners report spikes of
both conventional (sodium, nickel and vanadium) and unconventional metals (iron and calcium)
when running tight oil-derived feeds. Sodium and vanadium deactivate zeolite and suppress
activity; nickel promotes dehydrogenation reactions, leading to high gas make. Unconventional
metals such as iron and calcium deposit on the catalyst surface and cause a loss of diffusivity,
which leads to a loss in conversion and an increase in coke and bottoms. To maximize
profitability with rapidly changing feed quality, catalyst flexibility is key.

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6.0 CATALYTIC SOLUTIONS
Flexible catalyst functionality is critical for processing unconventional feeds and mitigating the
associated processing challenges. Grace’s newest FCC catalyst family, that of ACHIEVE™
catalysts, is designed to provide refiners that flexibility. Figure 7 summarizes the challenges
posed by tight oils and the catalyst technology solutions for mitigating them.

ACHIEVE™ features an optimized matrix technology to provide coke-selective bottoms

conversion without a gas penalty. The technology in the high diffusivity matrix of the
ACHIEVE™ catalyst is based on technology embodied in the popular MIDAS® catalyst, which
has been commercially proven to be more iron tolerant than competitive offerings. ACHIEVE™
FCC catalyst incorporates best-in-industry metals traps for nickel and vanadium, which are
highly effective to minimize coke and gas formation from these conventional metals.
ACHIEVE™ FCC catalyst also contains ultra-stable zeolite that retains activity in the face of
contaminant metals spikes. ACHIEVE™ catalyst can be formulated over a range of activity,
rare-earth exchange, and isomerization activities, to deliver an optimal balance of gasoline yield
to LPG while maintaining an optimum level of butylenes for the alkylation unit. Increasing
catalyst activity, via zeolite or rare-earth exchange can alleviate a circulation constraint and
restore the heat balance to a comfortable level. ZSM-5 based additives can be used to boost
octane, but the associated yield of propylene is not always desirable. A better solution is to
boost zeolite isomerization activity within the catalyst to selectively increase the yield of FCC
butylene and iso-butane, keeping the alkylation unit full and maintaining refinery pool octane.
The following examples illustrate how the flexibility of the ACHIEVE™ catalyst family can
address the challenges posed by tight oil.

6.1 Iron and Calcium Tolerance

Iron and calcium have a negative effect on catalyst performance. While particulate tramp iron
from rusting refinery equipment does not have a significant detrimental effect on catalyst, finely
dispersed iron particles in feed (either as organic compounds or as colloidal inorganic particles)
can deposit on the catalyst surface, reducing its effectiveness [23, 24]. The iron deposits
combine with silica, calcium, sodium and other contaminants to form low melting temperature
phases, which collapse the pore structure of the exterior surface, blocking feed molecules from
entering the catalyst particle and reducing conversion [25]. Iron in combination with calcium
and/or sodium has a greater negative effect on catalyst performance than iron alone. The
symptoms of iron and calcium poisoning include a loss of bottoms cracking, as feed particles
are blocked from entering the catalyst particle, and a drop in conversion.

Catalyst design can be optimized to resist the effects of contaminant iron and calcium in tight oil
feedstocks. High alumina catalyst, especially catalyst with alumina-based binders and matrices,
such as Grace’s MIDAS® catalyst, are best suited to process iron- and calcium-containing feeds
due to their resistance to the formation of low-melting-point phases that destroy the surface pore
structure [26]. Optimum distribution of mesoporosity also plays a role in maintaining
performance because diffusion to active sites remains unhindered, despite high-contaminant
metals. The resistance of MIDAS® catalyst to iron and calcium poisoning has been
demonstrated in many commercial applications [26,27]. Figure 8 presents data from the

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application of Grace’s MIDAS® 638 catalyst in an operation running 100% tight oil and high
levels of iron. The switch to MIDAS® 638 catalyst reduced bottoms yield even when iron
contamination increased.

6.2 Nickel and Vanadium Tolerance

Grace has a long history of incorporating both nickel and vanadium metals trapping into the
catalyst system, mitigating the negative impacts of the metals. Nickel is trapped where it is
initially cracked onto the catalyst with a proprietary Grace alumina. The alumina absorbs the
nickel into the catalyst particle, forming a stable nickel aluminate that is no longer active for
dehydrogenation reactions. Grace has been highly successfully in utilizing this technique.
Currently 65+% of our worldwide customers are taking advantage of this technology.

For vanadium trapping, incorporation of a trap in the catalyst system can provide widely
dispersed trapping capability, more effectively reducing the negative impacts of the
contaminant. Grace’s IVT-4 is an integral rare-earth based vanadium trap that converts
contaminant vanadium into an inert rare-earth vanadate, greatly reducing zeolite deactivation
and coke and gas production. Grace is currently using IVT-4 in 60%+ of our worldwide catalyst
formulations.

An example of the excellent metals trapping performance of the ACHIEVE™ catalyst system is
shown in Figure 9, which plots Ecat selectivities of ACHIEVE™ catalyst versus a competitive
base. The refiner was processing tight oil along with a shifting mix of opportunity crudes and
needed a catalyst with better metals tolerance. At the same Ecat nickel equivalents, the
ACHIEVE™ catalyst resulted in lower coke, lower gas and lower hydrogen than the competitive
base. Figure 10 presents box plots based on refinery operating data from the reformulation
showing that ACHIEVE™ catalyst resulted in higher gasoline yields and lower hydrogen, delta
coke and slurry yield. The superior metals tolerance of the ACHIEVE™ catalyst allowed the
refiner to increase conversion without increasing catalyst addition rate. The changes in
operating conditions and yields after moving to ACHIEVE™ catalyst are summarized in Table 7.
Applying typical Gulf Coast economics, the increase in gasoline yield and drop in slurry resulted
in a benefit of ~$0.70/bbl for the refinery.

6.3 Maintaining Heat Balance

When processing very light tight oil-derived feedstocks, insufficient catalytic activity requires that
the catalyst circulation rate increase so that conversion, and thus the coke yield from the
catalyst, increases to satisfy the FCC heat balance. If the FCCU cannot physically circulate
enough catalyst, it will be necessary to either reduce the unit charge rate or the reaction severity
to stay within the FCC catalyst circulation limit. Alternatively, refiners can satisfy the heat
balance by blending in a heavier feedstock, recycling slurry, burning torch oil, increasing
regenerator air preheat, or derating the stripping steam. However, these options often have a
detrimental effect on the operation [28, 29]. Table 8 summarizes the operating changes that
can be made to maintain heat balance and the potential issues of each change. The best way
to satisfy the heat balance with a very light feedstock is via proper application of catalyst
technology.

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As an example of the role of catalyst activity in maintaining heat balance, consider an FCC unit
operating on standard VGO which is contemplating a move to lighter tight oil feed type. Figure
11 presents pilot plant data of catalyst to oil ratio as a function of coke and conversion on the
two feedstocks. The base case catalytic coke of 2.5 wt% requires a C/O of about 5.5 and
results in 74% conversion. In order to keep the 2.5% coke yield with the lighter tight oil feed, a
C/O ratio of over 8.0 is necessary with an increase in conversion to about 77%. Most FCC units
are not capable of this dramatic increase in the catalyst circulation rate and the catalyst
circulation hydraulics will likely limit the unit severity or throughput.

In this same example, we consider a catalyst reformulation to a more active catalyst with a
different coke to conversion relationship as seen in Figure 12. Here, Catalyst A is applied and a
much more modest C/O of 6.5 is required to satisfy the coke yield, due to the inherent catalyst
activity of Catalyst A. Because of the coke to conversion relationship of Catalyst A, higher
conversion is achieved.

Using a high activity catalyst is required to counter the effects of low delta coke, but it is
important to select a catalyst with the proper coke selectivity (coke to conversion relationship).
ACHIEVE™ catalyst can be formulated with ultra-high activity zeolite to counter the effects of
low delta coke, while delivering the proper coke selectivity (coke to conversion relationship).
Grace has had multiple experiences with reformulations for processing lighter feeds from tight
oil or traditional hydrotreated FCC feed. In one commercial application, a refiner switched from
a competitive catalyst designed for high activity to Grace’s ACHIEVE™ catalyst. Feed and
catalyst properties are presented in Table 9. The feed was light and paraffinic with an API of
29.5. Table 10 presents yields at constant conversion based on testing of feed and equilibrium
catalyst from the unit. At constant conversion, the switch to ACHIEVE™ catalyst resulted in
higher activity, higher gasoline, higher LCO, lower bottoms, and improved coke selectivity.
Table 11 presents yields at constant coke. At constant coke, the switch to ACHIEVE™ catalyst
resulted in higher activity, higher gasoline and lower bottoms and an economic uplift of
~$0.40/bbl.

6.4 Maintaining Refinery Pool Octane

A common challenge reported by refiners operating on unconventional feeds, such as shale or
tight oil, is a loss of gasoline pool octane, caused by reduced volume of alkylation feedstock.
Within the ACHIEVE™ catalyst family, ACHIEVE™ 400 catalyst is formulated with multiple
zeolites with tailored acidity, to deliver an optimum level of butylenes to keep the alkylation unit
full and maintain refinery pool octane. Incorporation of isomerization activity into the catalyst
particle itself results in a more desirable yield pattern than would be realized by use of a
traditional octane boosting FCC additive. In addition, ACHIEVE™ 400 has been shown to
increase the octane of FCC naphtha.

An example of the yield shifts that are possible with this technology is found in Table 12, which
presents yields based on DCR™ pilot plant testing of base MIDAS® catalyst, MIDAS® catalyst
with added conventional ZSM-5 based OlefinsMax® additive, and ACHIEVE™ 400 catalyst with
multiple zeolite technology. The physical properties of the fresh catalysts in the study are given

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in Table 13. With traditional ZSM-5 technology, cracking of gasoline olefins continues past C7
into the C6 and generates a disproportionate amount of propylene relative to butylenes as
shown in Figure 13. Figure 14 presents the difference in olefins yields by carbon number versus
the base case for the ACHIEVE™ catalyst and the MIDAS® catalyst with OlefinsMax® additive.
Olefins cracking for the ACHIEVE™ 400 catalyst stopped at C7 olefins (as seen by the
ACHIEVE™ 400 catalyst producing the same level of C6 olefins as the base case), while the
use of ZSM-5 additive resulted in cracking of C6 olefins, as seen by the drop relative to the base
case. The newly developed dual-zeolite technology in ACHIEVE™ 400 works synergistically
with Grace’s high diffusivity matrix, to selectively enhance olefinicity, preferentially cracking
gasoline olefins at C7 and above into butylene. The result is a higher ratio of C4 to C3 olefin
yield than separate light olefins additives. Figure 15 illustrates the butylene selectivity
improvement of ACHIEVE™ 400 catalyst compared to a system using conventional ZSM-5
based additive.

At constant conversion, ACHIEVE™ 400 catalyst delivers higher gasoline octane and higher
LPG olefins, with preferentially more butylenes over propylene. The net result is higher total
octane barrels for the refinery. Figure 16 presents plots of RON and MON versus conversion,
showing that the ACHIEVE™ 400 catalyst results in higher gasoline octane than the base
MIDAS® catalyst and the MIDAS® catalyst with added conventional ZSM-5 based OlefinsMax®
additive. As seen in Figure 17, coke and bottoms are equivalent between the base case and
the ACHIEVE™ 400 catalyst, demonstrating that the increased butylenes selectivity was
realized without compromising the bottoms conversion activity of the catalyst. The distribution
between different butylene isomers is the same with ACHIEVE™ 400 catalyst as with the
MIDAS® catalyst with added conventional ZSM-5 based OlefinsMax® additive, as seen in Figure
18.

The octane number of gasoline is determined by the hydrocarbon types present in the gasoline.
While there are complex blending interactions between the different hydrocarbon types, the
general effect of hydrocarbon type on octane can be seen in pure component octane data.
Figure 19 presents pure component RON and MON values by carbon number for different
hydrocarbon families based on data from API Technical Project 45 [31]. In cases where more
than one isomer is present, an average of the octane values for the different isomers was used.
As seen in the figures, aromatics and olefins have roughly equivalent octanes, while
naphthenes, iso-paraffins and normal paraffins have lower octane numbers. The octane
numbers of olefins and aromatics are relatively unchanged with carbon number, while those of
naphthenes, iso-paraffins and normal paraffins drop as the chain length grows. In addition to
hydrocarbon type (olefin, paraffin, aromatic, etc.), the degree of branching within a molecule
affects octane. As an example, for C6 olefins, the straight chain molecule 1-hexene has a RON
of 76, the single branched molecule 2-methyl-1-pentene has a RON of 94, and the doubly
branched molecule 2,3-dimethyl-2-butene has a RON of 97 [31]. The octane enhancement
from the ACHIEVE™ 400 catalyst is from increased gasoline olefins and from increased olefins
isomerization. In Table 12, the PIANO data show that the ACHIEVE™ 400 catalyst has a
higher olefins concentration in the gasoline than the MIDAS® catalyst base case or the MIDAS®
catalyst with OlefinsMax® additive. The degree of olefins branching of gasoline in the DCR™

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study is presented in Figure 20. The gasoline olefins produced by the ACHIEVE™ 400 catalyst
were more highly branched, resulting in higher naphtha octane.

The increased butylene selectivity of ACHIEVE™ 400 catalyst can help refiners address the
potential octane debits associated with light paraffinic tight oil feeds. Figure 21 presents plots of
the annualized value of improved butylene selectivity for a 50,000 BBL/day FCCU based on
several butylene to gasoline value differentials. For a hypothetical 50,000 bbl/day FCCU where
butylene is valued at $45/bbl over gasoline, each 0.1 wt% increase in butylene selectivity results
in >$0.8MM/yr more value.

7.0 Conclusion
The tight oil boom has resulted in a renaissance in the North American refining industry. While
tight oils are generally light and sweet and easy to crack, quality can vary greatly and tight oil
derived feeds can contain sediments with high levels of iron and alkali metals. The light nature
of these feeds can result in difficulty maintaining heat balance and the paraffinic nature of the
feed slate can result in octane debits in the refinery. Proper catalyst choice allows refiners to
fully exploit the opportunity of tight oil while minimizing the detrimental impacts. Grace’s newest
catalyst family, ACHIEVE™ catalyst, is designed with the flexibility to enable refiners to
proactively respond to the opportunity of tight oil. The ACHIEVE™ catalyst family is currently in
commercial testing.

In addition to catalyst selection, an equally critical component to minimizing risks and challenges
associated with processing unconventional feeds is solid technical service support. Grace has
been providing industry-leading technical service to the refining industry since 1947. Grace
retains qualified, experienced engineers to support FCC customers by providing application and
operations expertise, as well as start-up and optimization assistance and industry
benchmarking. With the backing of advanced R&D facilities and high throughput testing labs,
let Grace’s technical service team help you assess potential challenges before they occur in
your FCCU via feed characterization, feed component modeling, and pilot plant studies.
Understanding feed impacts earlier provides an opportunity to optimize the operating
parameters and catalyst management strategies, enabling a more stable and profitable
operation.

Acknowledgements
The authors thank colleagues at Grace for assistance with the testing and analysis for this
paper. The many contributions of Olivia Topete to this paper are gratefully acknowledged.

References
[1] U.S. Energy Information Administration, “January 2014 Drilling Productivity Report for Key Tight
Oil and Shale Gas Regions,” released January 14, 2014.
[2] U.S. Energy Information Administration, “Annual Energy Outlook 2014 Early Release Overview,”
December 16, 2013.

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[3] U.S. Energy Information Administration, “Technically Recoverable Shale Oil and Shale Gas
Resources: An Assessment of 137 Shale Formations in 41 Countries Outside the United States,”
June 2013.
[4] BP, “BP Energy Outlook 2035,” January 2014.
[5] Marfone, P.A., “Refiners Have a New Learning Curve with Shale Oil,” Hydrocarbon Processing,
March 2013.
[6] Kremer, L., “Shale Oil Issues and Solutions,” AFPM Principles and Practices Session, Salt Lake
City, Utah, October 2012.
[7] Haynes, D., “Tight Oil Impact on Desalter Operations,” Crude Oil Quality Association Meeting,
New Orleans, Louisiana, November 2012.
[8] Ohmes, R., Routt, M., “Characterizing and Tracking Contaminants in Opportunity Crudes,” 2013
AFPM Annual Meeting, San Antonio, Texas.
[9] D. Hill, “North Dakota Refining Capacity Study Final Technical Report,” DOE Award No.: DE-
FE0000516, January 5, 2011.
[10] Platts Methodology and Specifications Guide, “The Eagle Ford Marker: Rationale and
Methodology,” October 2012.
[11] “Effects Of Possible Changes In Crude Oil Slate On The U.S. Refining Sector’s CO2 Emissions,”
prepared for the International Council On Clean Transportation by MathPro Inc., March 29, 2013.
[12] Haas, A., McElhiney, G., Ginzel, W., Buchsbaum, A., “Gasoline Quality- The Measurement of
Compositions and Calculation of Octanes,” Petrochem./Hydrocarbon Technol. 1990, 43, 21-26.
[13] Cotterman, R. L., Plumlee, K. W., “Effects of Gasoline Composition on Octane Number,” ACS
Meeting; Miami Beach, Florida, 1989.
[14] Savage, G., “Crude Preheat Management for Challenged and Unconventional Crudes,” Crude Oil
Quality Association Meeting, San Antonio, Texas, March 2013.
[15] Holubnyak, et. al., “Understanding the Souring at Bakken Oil Reservoirs,” SPE International
Symposium on Oilfield Chemistry, The Woodlands, Texas, April 2011.
[16] Cioppa, M.T., “Spatial Variations in Magnetic Components of the Devonian Birdbear Formation,
Williston Basin,” presented at the Geofluids VII Conference, Rueil-Malmaison, France, June
2012.
[17] Keyser, J.C., “Versatile Fluidized Bed Reactor,” US Patent 6,069,012, assigned to Kayser
Technology, 2000.
[18] Fitzharris, W.D., Ringle, S.J., Nicholes, K.S.,“Catalytic Cracking of Whole Crude Oil,” U.S. Patent
4,859,310 (1989), assigned to Amoco Corporation.
[19] Masologites, G.P., Beckberger, L.H., “Low-sulfur Syn Crude via FCC,” Oil and Gas Journal, 71
(1973), pp. 49-53.
[20] Bryden, K., Weatherbee, G., Habib, E.T., “Flexible Pilot Plant Technology for Evaluation of
Unconventional Feedstocks and Processes AM-13-04,” 2013 AFPM Annual Meeting, San
Antonio, Texas.
[21] Chapter 6, “FCC Operation,” in The Grace Davison Guide to Fluid Catalytic Cracking, 1993.
[22] Ritter, R.E., “Light Cycle Oil from the FCC Unit AM-88-57,” 1988 NPRA Annual Meeting, San
Antonio, Texas.
[23] Cheng, W.-C., Habib, E.T., Rajagopalan, K., Roberie, T.G., Wormsbecher, R.F., Ziebarth, M.S.,
“Fluid Catalytic Cracking,” in Handbook of Heterogeneous Catalysis, 2nd. Ed., 2008, pp. 2741-
2778.
[24] Yaluris, G., “The Effects of Fe Poisoning on FCC Catalysts: An Update,” Catalagram 91, W.R.
Grace & Co., 2002.
[25] Yaluris, G., Cheng, W.-C., Boock, L.T., Peters, M., Hunt, L.J., “The Effects of Fe Poisoning on
FCC Catalysts, AM-01-59” 2001 NPRA Meeting, New Orleans, Louisiana.

AM-14-16
Page 11
[26] Bryden, K.J., Habib, E.T., Topete, O.A., “Processing Shale Oils in FCC: Challenges and
Opportunities,” Hydrocarbon Processing, September 2013.
[27] Cher, Y.-Y., Koebel, J., Schiller, R., “Enhanced Bottoms Cracking and Process Flexibility with
®
Midas FCC Catalyst,” Catalagram 112, W.R. Grace & Co., 2012.
[28] Answers to Question 113, 2006 NPRA Q&A and Technology Forum, October 8-11, 2006,
Phoenix, AZ.
[29] Answers to Question 42, 2009 NPRA Q&A and Technology Forum, October 11-14, 2009, Fort
Worth, TX.
[30] Buchanan, J.S., Santiesteban, J.G., Haag, W.O., “Mechanistic Considerations in Acid-Catalyzed
Cracking of Olefins,” Journal of Catalysis, Volume 158, January 1996, Pages 279-287.
[31] Knocking characteristics of pure hydrocarbons, Developed Under American Petroleum Institute
Research Project 45, Special Technical Publication No. 225; American Society for Testing and
Materials: West Conshohocken, PA, 1958.
[32] Schipper, P. H., Dwyer, F.G., Sparrell, P.T., Mizrahi, S., Herbst, J.A., “Zeolite ZSM-5 in Fluid
Catalytic Cracking: Performance, Benefits, and Applications.” In Fluid Catalytic Cracking, edited
by Mario L. Occelli, 375:64–86. Washington, DC: American Chemical Society, 1988.

GRACE®, MIDAS®, G-Con® and OLEFINSMAX® are trademarks, registered in the United States and/or
other countries, of W. R. Grace & Co.-Conn. DCR™ and ACHIEVE™ are trademarks of W. R. Grace &
Co.-Conn. This trademark list has been compiled using available published information as of the
publication date of this brochure and may not accurately reflect current trademark ownership or status.
GRACE CATALYSTS TECHNOLOGIES is a business segment of W. R. Grace & Co.-Conn., which now
include all catalyst product lines formerly sold under the GRACE DAVISON brand. © Copyright 2014 W.
R. Grace & Co.-Conn. All rights reserved.

AM-14-16
Page 12
Figure 1. Scanning electron micrograph of sediment filtered from whole Bakken crude.

AM-14-16
Page 13
Figure 2. Energy dispersive spectroscopy maps of sediment in Bakken crude.

Fe

Ca S

AM-14-16
Page 14
Figure 3. Yield structure of starting feeds and cracked products for straight run Bakken and mid-
continent VGO (970°F riser outlet temperature in circulating riser pilot plant.)

100

90
Weight Percent Fresh Feed

80

70

60
Dry Gas
50 LPG
Gasoline (C5-430°F)
40 LCO (430-650°F)
Bottoms (650°F+)
30
Coke
20

10

0
Straight Run Bakken Cracked Mid-Continent Mid-Continent
Bakken at 970°F ROT VGO cracked at VGO
970°F

AM-14-16
Page 15
Figure 4. Product yields as a function of riser outlet temperature and feed.

C/O Ratio C5+ Gasoline wt%

70
10

65
8

60
6
55
4
Bakken 900°F
50 Bakken 935°F
LCO (430-650F) wt% Coke wt%
Bakken 970°F
20.0 4 VGO 970°F

17.5
3

15.0
2
12.5

10.0 1
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
Conversion wt%

AM-14-16
Page 16
Figure 5. Gasoline properties as a function of riser outlet temperature and feed.

G-Con RON EST G-Con MON EST

95 80

90
75
85

80 70
Bakken 900°F
75 Bakken 935°F
65 Bakken 970°F
G-Con O wt% G-Con I wt%
VGO 970°F
35 26

30
24
25

20 22

15
20
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
Conversion wt%

AM-14-16
Page 17
Figure 6. Effect of conversion level and feed type on LCO yield and quality.

LCO (430-650F) wt% Diesel Index

22 50

20
40

18
30 Bakken 900°F
Bakken 935°F
16 Bakken 970°F
VGO 970°F
20
14

10
12

10 0
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
Conversion wt%

AM-14-16
Page 18
Figure 7. Challenges posed by tight oil feedstocks, their consequences, and the catalytic
solutions.

Challenge Consequence Catalyst Solution

Loss of Bottoms Cracking

Fe and Ca Poisoning Employ a High Porosity Matrix
and Conversion
Loss of Surface Area
Unpredictable Swings Utilize Traps for Ni and V with
Leads to Lower MAT and
in Contaminant Metals High Stability Zeolites
Conversion
Low Regenerator Temps,
FCC Heat Balance Increase Catalyst Activity
Circulation Constraints

Lower Severity to Control Boost Zeolite Isomerization

Refinery Imbalances
LPG Reduces Octane Activity

AM-14-16
Page 19
Figure 8. MIDAS® 638 Catalyst Maintains Selectivity in 100% Tight Oil Operation.

ECAT Fe, wt%

1.15
1.10
1.05
1.00
0.95
0.90
Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar-14
Base MIDAS® 638

Bottoms Yield, wt%

10.5
9.5
8.5
7.5
6.5
5.5
Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar-14
Base MIDAS® 638

AM-14-16
Page 20
Figure 9. ACHIEVE™ catalyst delivers superior metals tolerance compared to a competitive
base.

Coke Factor Gas Factor

2.0 6

1.8

5
1.6

1.4
4
1.2
H2 Yield, SCFB 2400 2550 2700 2850 3000
360

320 Competitive Base

ACHIEVE™ Catalyst
280

240

200

2400 2550 2700 2850 3000

ECAT Ni equivalents, ppm

AM-14-16
Page 21
Figure 10. Unit data demonstrating improved performance of ACHIEVE™ catalyst versus the
competitive base.

Hydrogen, SCFB Conversion, vol.% Gasoline, vol.%

20 6
4
4
0 2
2

0
-20 0

-2 -2
-40
Gasoline + LCO, vol.% Slurry, vol.% Delta Coke
3.0 0.2
2

1.5
0.0
0
0.0

-1.5 -0.2
-2

-3.0
Competitiv e Base ACHIEVE™ Cataly st Competitiv e Base ACHIEVE™ Cataly st Competitiv e Base ACHIEVE™ Cataly st

AM-14-16
Page 22
Figure 11. Comparison of a base VGO feed to a lighter tight oil type feed.

9.0 9.0

8.0 8.0
Cat-to-Oil Ratio

7.0 7.0

6.0 6.0

5.0 5.0

4.0 4.0

3.0 3.0
1.0 2.0 3.0 4.0 64.0 68.0 72.0 76.0 80.0
Coke, wt% Conversion, wt%

Base - VGO feed FEED

Light SO
Tight Oil Feed

AM-14-16
Page 23
Figure 12. Effect of change in catalyst activity on catalyst to oil requirements to maintain
constant coke.

9.0 9.0

8.0 8.0
Cat-to-Oil Ratio

7.0 7.0

6.0 6.0

5.0 5.0

4.0 4.0

3.0 3.0
1.0 2.0 3.0 4.0 64.0 68.0 72.0 76.0 80.0
Coke, wt% Conversion, wt%
Base - VGO feed Light SO
FEED Tight Catalyst A
Oil Feed

AM-14-16
Page 24
Figure 13. ACHIEVE™ 400 catalyst preferentially cracks gasoline olefins at C7 and above.

Relative
Reactant Selectivity Reactivity C3=/C4=

ACHIEVE™ 400
2 C4= 44%
C8= 100 0.64
C3= + C5= 56%

ZSM-5 Additive
C3= + C4= 95%
C7= 12 1.0
C2= + C5= 2%

2 C3= 83%
C6= 1.5 11
C2= + C4= 16%

Buchanan, et. al., Ref. 30

AM-14-16
Page 25
Figure 14. Incremental olefin yields by carbon number relative to base Midas® Catalyst at
constant conversion demonstrate that ACHIEVE™ 400 catalyst does not crack C6 olefins as
ZSM-5 based additives do.

1.5

1
Delta Olefins, wt% FF

0.5
Base MIDAS® Catalyst +
OlefinsMax® Additive
ACHIEVE™ 400 Catalyst
0
2 3 4 5 6 7 8 9

-0.5

-1
Carbon Number

AM-14-16
Page 26
Figure 15. At constant conversion ACHIEVE™ 400 delivers a higher ratio of ΔC4 to ΔC3 olefins
than use of a separate ZSM-5 based olefins additive.

1.4

1.2
Δ C4=

0.8

0.6
0.6 0.8 1 1.2 1.4
Δ C3=

Base MIDAS® + OlefinsMax® ACHIEVE™ 400

AM-14-16
Page 27
Figure 16. RON and MON at constant conversion for three catalyst systems.

94.6

94.4

94.2

94.0
RON

93.8

93.6

93.4

93.2

93.0
70 72 74 76 78
Conversion, wt%

Base Midas® Base Midas® + OlefinsMax® ACHIEVE™ 400

80.6

80.4

80.2

80.0
MON

79.8

79.6

79.4

79.2

79.0
70 72 74 76 78
Conversion, wt%

Base Midas® Base Midas® + OlefinsMax® ACHIEVE™ 400

AM-14-16
Page 28
Figure 17. Coke to bottoms relationship for ACHIEVE™ 400 Catalyst compared to base
MIDAS® Catalyst.

10

9
Bottoms wt%

5
5.5 6 6.5 7 7.5 8
Coke wt%
Base Midas® Base Midas® + OlefinsMax® ACHIEVE™ 400

AM-14-16
Page 29
Figure 18. Distribution of butylene isomers for ACHIEVE™ 400 and Base Midas® +
OlefinsMax®.

40%

30%
% Total C4=

20%

10%

0%
cC4= tC4= iC4= 1-C4=
Base Midas® + OlefinsMax® ACHIEVE™ 400

AM-14-16
Page 30
Figure 19. Pure component RON and MON as a function of hydrocarbon type and carbon
number. (Based on API Research Project 45.)

140
Research Octane Number

120

100

80

60

40

20

-20

-40

-60

-80
2 4 6 8 10 12 14
Carbon Number
Aromatics Olefins Naphthenes monomethyl-iso-paraffins n-paraffins

120

100
Motor Octane Number

80

60

40

20

-20

-40

-60

-80
2 4 6 8 10 12 14
Carbon Number
Aromatics Olefins Naphthenes monomethyl-iso-paraffins n-paraffins

AM-14-16
Page 31
Figure 20. ACHIEVE™ 400 Catalyst Results in increased C5 and C6 olefins branching.

0.63
C5= branched / C5= total

0.62

0.61

0.6
ACHIEVE™ 400 Catalyst
0.59
Base MIDAS® Catalyst +
0.58 OlefinsMax® Additive
Base MIDAS® Catalyst
0.57

0.56

0.55
70 72 74 76 78
conversion, wt%

0.52
C6= branched / C6= total

0.51
0.5
0.49
0.48 ACHIEVE™ 400 Catalyst
0.47
Base MIDAS® Catalyst +
0.46 OlefinsMax® Additive
0.45 Base MIDAS® Catalyst
0.44
0.43
0.42
70 72 74 76 78
conversion, wt%

AM-14-16
Page 32
Figure 21. Annualized value of improved butylene selectivity for a 50,000 BBL/day FCCU.

$6,000,000

$5,000,000

Value differential
Annualized Value

between C4=
$4,000,000
and gasoline

$60/BBL
$3,000,000
$45/BBL
$30/BBL
$15/BBL
$2,000,000

$1,000,000

$0
0 0.1 0.2 0.3 0.4 0.5 0.6
Uplift from gasoline to C4= (percent)

AM-14-16
Page 33
Table 1. Properties of straight run tight oil feed used in this study compared to publically
published assay data.

Published assay data

Bakken
sample
used in “Typical”
Bakken
this work WTI [9] LLS [9] Eagle Ford
[9]
[10, 11]
API Gravity Degrees 41.9 >41 40.0 35.8 47.0
Sulfur wt% 0.19 <0.2 0.33 0.36 0.11
Distillation Yield Weight % Volume% Volume% Volume% Volume%
Light Ends C1-C4 1 3 1 2 1
Naphtha C5-330°F 32 30 30 17 34
Kerosene 330-450°F 14 15 15 14 15
Diesel 450-680°F 25 25 24 34 23
Vacuum Gas Oil 680-1000°F 23 22 23 25 20
Vacuum Residue 1000+°F 5 5 7 8 7
Total 100 100 100 100 100
Conradson
wt% 0.78
Carbon Residue
Gasoline
Fraction RON (G-Con) 60.6
Properties
MON (G-Con) 57.6
LCO Fraction
Aniline point
(430°F - 650°F) 155.9
(°F)
properties
API Gravity 37.6
Diesel Index 58.6

AM-14-16
Page 34
Table 2. Properties of tight oil derived FCC feeds compared to typical mid-continent vacuum
gas oil.

430°F+ 650°F+
Eagle Ford HVGO
Distillation Distillation Mid-
Condensate Derived
Property of Whole of Whole Continent
Splitter from 85%
Bakken Bakken VGO
Bottoms Eagle Ford
Crude Crude
API Gravity (degrees) 36.6 30.0 28.6 23.0 24.7
CCR (wt%) 0.15 0.17 1.34 2.27 0.32
K-Factor 12.48 12.39 11.73 11.86 12.01
Sulfur (wt%) 0.08 0.83 0.3 0.43 0.35
Basic Nitrogen (wt%) 0.00 0.02 0.02 0.04 0.05
Hydrogen (wt%) 13.7 13.4 13.1 12.7 12.9
Percent Boiling >1000°F 10.7 13.1 14.5 23.6 16.5
Molecular Weight 373 455 321 414 430
n-d-m analysis
Ca, Aromatic Ring Carbons (%) 14.8 15.2 16.9 22.1 17.6
Cn, Naphthenic Ring Carbons (%) 19.4 9.8 21.7 17.3 20.3
Cp, Paraffinic Carbons (%) 65.8 75.0 61.4 60.6 62.1
D2887 Simulated Distillation (°F)
Initial Boiling Point 266 597 330 530 527
10% 519 715 470 658 691
20% 599 762 524 711 734
30% 649 797 580 756 773
40% 693 830 638 798 810
50% 735 862 699 844 848
60% 780 895 767 895 886
70% 835 929 840 953 928
80% 907 967 931 1027 976
90% 1006 1015 1057 1135 1045

AM-14-16
Page 35
Table 3. HRMS 22-Component Hydrocarbon Types Analysis of two tight oil derived FCC feeds
compared to a typical mid-continent vacuum gas oil.

650°F+ Mid-
Eagle Ford
Distillation of Continent
Condensate
Whole VGO
Splitter
Bakken
Bottoms
Crude
AVE WT % AVE WT % AVE WT %
SATURATES
C(N)H(2N+2) Paraffins 44.4 12.4 12.2
C(N)H(2N) Monocycloparaffins 25.5 27.8 25.5
C(N)H(2N-2) Dicycloparaffins 8.9 12.5 11.0
C(N)H(2N-4) Tricycloparaffins 5.8 6.5 6.1
C(N)H(2N-6) Tetracycloparaffins 2.1 0.0 0.0
C(N)H(2N-8) Pentacycloparaffins 0.7 0.0 0.0
TOTAL SATURATES 87.6 59.2 54.7
MONOAROMATICS
C(N)H(2N-6) Alkylbenzenes 3.1 10.8 10.5
C(N)H(2N-8) Benzocycloparaffins 0.8 6.0 6.3
C(N)H(2N-10) Benzodicycloparaffins 1.2 4.2 3.7
DIAROMATICS
C(N)H(2N-12) Naphthalenes 1.1 2.6 3.8
C(N)H(2N-14) 1.2 2.0 4.2
C(N)H(2N-16) 2.2 3.9 6.4
TRIAROMATICS
C(N)H(2N-18) 1.5 3.1 4.6
C(N)H(2N-22) 0.2 4.3 2.4
TETRAAROMATICS
C(N)H(2N-24) 0.0 1.4 0.1
C(N)H(2N-28) 0.0 0.0 0.0
TOTAL AROMATICS 11.3 38.3 41.9
THIOPHENIC COMPOUNDS
C(N)H(2N-4)S Thiphenes 0.0 0.0 0.0
C(N)H(2N-10)S Benzothiophenes 0.7 1.6 2.3
C(N)H(2N-16)S Dibenzothiophenes 0.5 0.8 1.1
C(N)H(2N-22)S Naphthobenzothiophenes 0.0 0.0 0.0
TOTAL THIOPHENIC COMPOUNDS 1.1 2.4 3.4

AM-14-16
Page 36
Table 4. Metals analysis of several tight oils.

Published Assay
Samples in this paper Published Assay Data (Ref 14)
Data (Ref 7)
650°F+ Eagle Ford 75% Eagle
Mid- Whole Flashed 75% Eagle
Distillation of Condensate Ford Bakken Eagle Ford
Property Continent Bakken Bakken Ford Stream
Bakken Splitter Stream Crude Crude
VGO Crude Crude (filtered)
Crude Bottoms (total)
not not
Barium (ppm) <0.01 0.2 0.1 0.8 not reported 0.02 0.21
reported reported
Calcium (ppm) <0.1 0.5 1.2 5.4 0.6 15 1.4 0.54 9.8
Iron (ppm) <0.1 7.5 7.8 8.6 4.1 16 3 0.7 2.3
Magnesium (ppm) <0.04 0.2 0.2 0.3 <0.2 1.6 <0.12 0.05 0.34
Nickel (ppm) <0.04 0.4 1.9 0.2 0.6 8 8 0.05 <0.14
Potassium (ppm) <0.04 0.4 0.3 0.0 <0.2 1.2 <0.3 0.1 0.5
Sodium (ppm) <0.06 8.7 3.9 3.1 4.1 34 0.4 2.8 12
Vanadium (ppm) <0.03 0.1 0.5 0.9 0.22 22 22 0.02 <0.05

AM-14-16
Page 37
Table 5. Deactivated catalyst properties

Total Surface Area (m²/g) 196

Zeolite Surface Area (m²/g) 110
Matrix Surface Area (m²/g) 86
Unit Cell Size (Å) 24.30
Rare earth (wt%) 2.1
Alumina (wt%) 52.1

AM-14-16
Page 38
Table 6. Interpolated yields at C/O = 6 for five tight oil derived feedstocks compared to Mid-
Continent VGO.

HVGO Eagle Ford

Whole 430°F+ 650°F+ Mid
Derived Condensate
Bakken Distillation Distillation Continent
from 85% Splitter
Crude of Bakken of Bakken VGO
Eagle Ford Bottoms
Conversion (wt %) 83.5 71.7 74.3 74.4 83.3 86.3
H2 Yield (wt%) 0.02 0.06 0.08 0.04 0.09 0.05
C1's+C2's (wt%) 0.9 1.2 1.5 1.3 1.3 1.0
Total C3 (wt%) 4.5 5.1 5.2 5.1 6.7 8.1
C3= (wt%) 3.5 4.4 4.4 4.4 5.8 7.0
Total C4's (wt%) 10.1 10.8 10.7 10.8 14.3 17.3
C4= (wt%) 4.3 5.7 5.9 6.1 8.2 9.4
LPG (wt%) 14.6 16.0 15.9 15.9 21.0 25.4
Gasoline (C5-430°F)
65.4 52.1 52.9 54.1 58.6 58.4
(wt%)
RON (G-Con) 78.0 89.2 90.1 90.3 90.8 89.1
MON (G-Con) 70.9 78.9 79.6 79.5 79.9 78.8
LCO (430-700°F)
14.2 24.6 19.6 19.1 12.2 11.5
(wt%)
Bottoms (700°F+)
2.3 3.7 6.0 6.4 4.5 2.2
(wt%)
Coke (wt%) 1.8 2.7 4.1 2.9 2.5 1.3

AM-14-16
Page 39
Table 7. Changes in operating commercial conditions and resulting yields versus competitive
base catalyst after application of metals tolerant ACHIEVE™ catalyst.

Delta (ACHEIVE™-
Competitive Base)
Operating Parameters
Relative Fresh Feed Rate -4%
Feed Temp, °F -72°F
Feed API Same
Reactor Temp, °F +6°F
Regen Dense, °F -1°F
Regen Dilute, °F +3°F
Catalyst Additions, lbs/bbl Same
Yields
Coke, wt.% +0.1
Delta Coke, wt.% -0.06
430°F conversion, vol% +3.8
H2, SCFB -20
Dry Gas, vol.% Same
C3, vol.% +1.2
C4, vol.% +1.4
Gasoline vol.% +2.1
LCO, vol.% -1.7
Slurry Yield, vol.% -2.1

AM-14-16
Page 40
Table 8. Options for maintaining heat balance with light feeds.

Option Potential Issues

Availability of heavier feedstock. Crude
Blend in heavier feedstock incompatibility and asphaltene precipitation.
High metals in heavier crudes.
Increased energy consumption. Metallurgical
Increase feed preheat limits. Increase in non-selective thermal
cracking and dry gas production.
Feed system fouling. Catalyst erosion.
Slurry recycle
Increased dry gas yield.
Accelerated catalyst deactivation. Burning of a
Burning torch oil in the regenerator
high value stream.
Wear of stripper steam rings. Stripper steam
Reduce stripping steam rate
plugging. Accelerated catalyst deactivation.
Increase preheat of regenerator air Increased catalyst and air grid nozzle attrition.
Best and most profitable option for maintaining
Increase FCC catalyst activity
heat balance.

AM-14-16
Page 41
Table 9. Feed and Catalyst Properties for Commercial Application of High Activity Catalyst with
Light Feed.

Feed Properties
API Gravity (degrees) 29.5
CCR (wt%) 0.29
K-factor 12.19
n-d-m analysis
Ca, Aromatic Ring Carbons (%) 13.9
Cn, Naphthenic Ring Carbons (%) 16.9
Cp, Paraffinic Carbons (%) 69.2
Equilibrium Catalyst Properties
Competitive Base ACHIEVE™ Catalyst
Surface Area (m2/g) 164 154
Ni (ppm) 176 203
V (ppm) 892 1022

AM-14-16
Page 42
Table 10. ACHIEVE™ catalyst outperforms competitive technology in a light feed application-
yields at constant conversion.

Competitive Base ACHIEVE™

C/O Ratio 6.9 5.8
Conversion, wt% 76.0 76.0
H2 Yield, wt% 0.05 0.04
Dry Gas, wt% 1.0 1.0
Propylene, wt% 4.5 4.4
Total C3’s, wt% 5.6 5.5
Total C4=s, wt% 5.5 5.5
Total C4s, wt% 12.7 12.4
Gasoline, wt% 54.2 54.9
LCO, wt% 17.2 17.6
Bottoms, wt% 6.8 6.4
Coke, wt% 2.7 2.5

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Table 11. ACHIEVE™ catalyst outperforms competitive technology in a light feed application-
yields at constant coke.

Competitive Base ACHIEVE™

Coke, wt% 2.7 2.7
C/O Ratio 6.9 6.4
Conversion, wt% 76.0 77.4
H2 Yield, wt% 0.05 0.05
Dry Gas, wt% 1.0 1.0
Propylene, wt% 4.5 4.5
Total C3’s, wt% 5.6 5.7
Total C4=s, wt% 5.5 5.5
Total C4s, wt% 12.7 12.9
Gasoline, wt% 54.2 55.3
LCO, wt% 17.2 16.9
Bottoms, wt% 6.8 5.7

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Table 12. ACHIEVE™ 400 Catalyst provides higher octane and more C4 olefins than using
ZSM-5 additive.

®
Base Midas
Base Catalyst TM
® ACHIEVE 400
Midas +
Catalyst
® Catalyst
OlefinsMax
Additive
Cat to Oil 8.7 9.2 8.3
Dry gas, wt% 2.84 2.78 2.75
C3=, wt% 4.3 5.1 5.3
Total C4s, wt% 9.3 10.2 10.6
iC4, wt% 1.5 1.7 1.6
nC4, wt% 0.4 0.4 0.4
Total C4= wt% 7.3 8.1 8.5
ΔC4= / ΔC3= --- 0.89 1.1
Gasoline, wt% 50.8 49.1 48.7
LCO, wt% 18.4 18.2 18.2
Bottoms, wt% 6.6 6.7 6.7
Coke, wt% 6.9 6.8 6.7
G-Con RON 93.50 93.53 94.12
G-Con MON 79.69 79.80 80.07
G-Con P wt% 3.0 3.0 2.8
G-Con I wt% 18.5 18.5 17.9
G-Con A wt% 31.3 32.2 31.9
G-Con N wt% 10.9 10.7 10.2
G-Con O wt% 36.3 35.6 37.2

Note that there was little increase in RON when conventional ZSM-5 based OlefinsMax®
additive was used since the base RON was high (93.5) and the effect of ZSM-5 additive on
RON drops as base RON increases, as discussed in Reference 32.

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Table 13. Fresh catalyst properties.

®
Base Midas
® Catalyst TM
Base Midas ACHIEVE 400
+
Catalyst ® Catalyst
OlefinsMax
Additive
Al2O3, % 55.9 55.3 54.5
RE2O3, % 1.4 1.4 1.4
3
ABD, g/cm 0.70 0.67 0.70
APS, microns 78 76 75
2
ZSA, m /g 134 140 145
2
MSA, m /g 140 142 143

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