Grace Catalysts Technologies Catalagram® 3
Kenneth BrydenManager, FCC Evaluations Research
Michael FederspielNational Sales Leader,Americas
E. Thomas Habib, Jr.Director, Customer Research Partnershipsand DCR LicensingManager
Rosann SchillerMarketing Director,FCC Commercial Strategy
Grace Catalysts TechnologiesColumbia, MD, USA
AbstractTight 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.
IntroductionAs 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/day1. 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 advances and the rapid growth of tight oil production
have made forecasts difficult, the U.S. Energy Information Agency currently forecasts that United States
tight oil production will top 4.8 MM bbl/day in 20212. 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 global technically recoverable oil resources3. The January 2014 BP Energy
Processing Tight Oils in FCC: Issues, Opportunities and FlexibleCatalytic Solutions
4 Issue No. 114 / 2014
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 States4. 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.
Tight Oil PropertiesTight oil is highly variable. Density and other properties can show
wide variation, even within the same field5-8. Tight oils are
generally light, paraffinic and sweet. Table I 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 assays10. The Bakken crude is light and sweet with an API 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 APIs 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 a Grace’s proprietary G-Con® octane calculation
software based on detailed GC analysis12,13. 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 II presents properties of a 430°F+ distillation of Bakken, a
650°F+ distillation of Bakken, along with two Eagle Ford based
FIGURE 1: Scanning Electron Micrograph of Sediment Filtered from Whole Bakken Crude (pg. 6)
Grace Catalysts Technologies Catalagram® 5
Bakken sampleused in this work
Published Assay Data
Bakken (9) WTI (9) LLS (9) “Typical” EagleFord (10, 11)
API Gravity Degrees 41.9 >41 40 35.8 47.0
Sulfur Wt.% 0.19 <0.2 0.33 0.36 0.11
Distillation Yield Wt.% Vol.% Vol.% Vol.% Vol.%
Light Ends C1-C4 1 3 1 2 1
Naphtha C5-330˚F 32 30 32 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 100Conradson Carbon Residue Wt.% 0.78
Gasoline FractionProperties
RON (G-Con) 60.6
MON (G-Con) 57.6
LCO Fraction(430˚F-650˚F)Properties
Anline Point, ˚F 155.9
API Gravity 37.6
Diesel Index 58.6
TABLE I: Properties of Straight Run Tight Oil Feed Used in this Study Compared to Publically Published Assay Data
PropertyEagle Ford
CondensateSplitter Bottoms
HVGO Derived from 85%
Eagle Ford
430°F+ Distillation of Whole
Bakken Crude
650°F+ Distillation of Whole
Bakken Crude
Mid-ContinentVGO
API Gravity, ˚F 36.6 30.0 28.6 23.0 24.7
CCR, wt.% 0.15 0.17 0.34 2.27 2.32
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
TABLE II: Properties of Tight Oil Derived FCC Feeds Compared to Typical Mid-Continent Vacuum Gas Oil
6 Issue No. 114 / 2014
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 III 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 metals6,14.
Table IV presents metals analysis 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
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 a 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 (pg.4). Energy dispersive spectroscopy
maps of iron, sulfur and calcium are pictured in Figure 2. The iron
in the sediments is associated with the sulfur.
Eagle Ford Condensate
Splitter Bottoms
650°F+ Distillation of Whole
Bakken Crude
Mid-Continent VGO
Saturates AVE, wt.% AVE, wt.% AVE, wt.%
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
Tetra-aromatics
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 Thiophenes 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
TABLE III: HRMS 22-Component Hydrocarbon Types Analysis of Two Tight Oil Derived FCC Feeds Compared to aTypical Mid-Continent Vacuum Gas Oil
Grace Catalysts Technologies Catalagram® 7
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
formation15,16. 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.
Cracking Yields of Whole Tight Oiland 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
FIGURE 2: Energy Dispersive Spectroscopy Maps of Sediment in Bakken Crude
Samples in this Paper Published Assay Data14 Published AssayData7
PropertyMid-
ContinentVGO
Whole Bakken Crude
650°F+ Distillation of Bakken
Crude
Eagle Ford Condensate
Splitter Bottoms
Flashed Bakken Crude
75% Eagle Ford
Stream(total)
75% Eagle Ford
Stream (filtered)
Bakken Crude
Eagle Ford
Crude
Barium, ppm <0.01 0.2 0.1 0.8 not reported
not reported
not reported 0.02 0.21
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 04 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
TABLE IV: Metals Analysis of Several Tight Oils
8 Issue No. 114 / 2014
are presented in Tables I and II. Cracking was done over an FCC
catalyst in a fixed-fluidized bed ACE test unit17 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 V.
Interpolated yields at a catalyst-to-oil (C/O) ratio of 6 are
presented in Table VI. 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 it 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.
Processing Straight Run Tight Oil -Effect of Operating Variables onYields and Product PropertiesWhile 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 available due to maintenance
on other units in the refinery18, and to produce a low-sulfur
synthetic crude19.
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 I 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 II 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 V.
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+
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
TABLE V: Deactivated Catalyst Properties
Whole Bakken Crude
430°F+ Distillationof Bakken
650°F+ Distillation of Bakken
Mid-ContinentVGO
HVGO Derivedfrom 85%
Eagle Ford
Eagle Ford Condensate
Splitter 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), wt.% 65.4 52.1 52.9 54.1 58.6 58.4
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), wt.% 14.2 24.6 19.6 19.1 12.2 11.5
Bottoms (700°F+), wt.% 2.3 3.7 6.0 6.4 4.5 2.2
Coke, wt.% 1.8 2.7 4.1 2.9 2.5 1.3
TABLE VI: Interpolated Yields at C/O = 6 for Five Tight Oil Derived Feedstocks Compared to Mid-Continent VGO
Grace Catalysts Technologies Catalagram® 9
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 work21. 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.
Straight RunBakken
Bakken Crackedat 970˚F ROT
Mid-ContinentVGO Cracked
at 970˚F
Mid-ContinentVGO
Dry Gas LPG Gasoline (C5-430˚F) LCO (430-650˚F)
Bottoms (650˚F+) Coke
Wt.%
Fre
sh F
eed
100
90
80
70
60
50
40
30
20
10
0
FIGURE 3: DCR Yield Structure of Starting Feeds andCracked Products for Straight Run Bakken and Mid-Continent VGO (970°F Riser Outlet Temperature)
FIGURE 4: Product Yields as a Function of Riser Outlet Temperature and Feed
Conversion, wt.%
10
8
6
4
10.0
12.5
15.0
17.5
20.0
50
55
60
65
70
1
2
3
4
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
C/O Ratio
LCO (430-650˚F), wt.% Coke, wt.%
C5+ Gasoline, wt.%
Bakken 900˚F
Bakken 935˚F
Bakken 970˚F
VGO 970˚F
10 Issue No. 114 / 2014
FIGURE 5: Gasoline Properties as a Function of Riser Outlet Temperature and Feed
Bakken 900˚FBakken 935˚FBakken 970˚FVGO 970˚F
95
90
85
80
15
20
25
30
35
G-Con RON EST G-Con MON EST
G-Con I, wt.%G-Con O, wt.%
75
80
75
70
20
22
24
26
65
Conversion, wt.%
75.0 77.5 80.0 82.5 85.0 75.0 77.5 80.0 82.5 85.0
FIGURE 6: Effect of Conversion Level and Feed Type on LCO Yield and Quality
Bakken 900˚FBakken 935˚FBakken 970˚FVGO 970˚F
22
20
18
16
LCO (430-650˚F), wt.%
14
Conversion, wt.%
75.0 77.5 80.0 82.5 85.0 77.5 80.0 82.5 85.0
Diesel Index
75.0
12
10
50
40
30
20
10
0
Grace Catalysts Technologies Catalagram® 11
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 work22, 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 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.
Processing ChallengesLight 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.
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™ 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™ 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 alky 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.
12 Issue No. 114 / 2014
Iron and Calcium ToleranceIron 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 effectiveness23,24. 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 conversion25. 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 structure26. 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 applications26,27.
Figure 8 presents data from the 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.
FIGURE 7: Challenges Posed by Tight Oil Feedstocks, Their Consequences, and the Catalytic Solutions
Challenge Consequence Catalyst Solution
Fe and Ca Poisoning Loss of Bottoms Cracking and Conversion Employ a High Porosity Matrix
Unpredictable Swings in Contaminant Metals
Loss of Surface Area Leads to Lower MAT and
Conversion
Utilize Traps for Ni and V with High Stability Zeolites
FCC Heat Balance Low Regenerator Temps, Circulation Constraints Increase Catalyst Activity
Refinery Imbalances Lower Severity to Control LPG Reduces Octane
Boost Zeolite IsomerizationActivity
0.90
0.95
1.00
1.05
1.10
1.15ECAT Fe, wt%
5.5
6.5
7.5
8.5
9.5
10.5Bottoms Yield, wt%
Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar-14
Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar-14
Base MIDAS® 638
FIGURE 8: MIDAS® 638 Catalyst Maintains Selectivity in 100% Tight Oil Operation
Grace Catalysts Technologies Catalagram® 13
Nickel and Vanadium ToleranceGrace has a long history of incorporating both nickel and vanadiummetals trapping into the catalyst system, mitigating the negativeimpacts of the metals. Nickel is trapped where it is initially crackedonto the catalyst with a proprietary Grace alumina. The aluminaabsorbs the nickel into the catalyst particle, forming a stable nickelaluminate 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 advantageof this technology.
For vanadium trapping, incorporation of a trap in the catalystsystem can provide widely dispersed trapping capability, moreeffectively reducing the negative impacts of the contaminant.Grace’s IVT-4 is an integral rare-earth based vanadium trap thatconverts 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 catalystformulations.
An example of the excellent metals trapping performance of theACHIEVE™ catalyst system is shown in Figure 9, which plots Ecatselectivities of ACHIEVE™ catalyst versus a competitive base.The refiner was processing tight oil along with a shifting mix ofopportunity 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 thanthe competitive base. Figure 10 presents box plots based onrefinery operating data from the reformulation showing thatACHIEVE™ catalyst resulted in higher gasoline yields and lowerhydrogen, delta coke and slurry yield. The superior metalstolerance of the ACHIEVE™ catalyst allowed the refiner toincrease conversion without increasing catalyst addition rate. Thechanges in operating conditions and yields after moving toACHIEVE™ catalyst are summarized in Table VII. Applying typicalGulf Coast economics, the increase in gasoline yield and drop inslurry resulted in a benefit of ~$0.70/bbl for the refinery.
Maintaining Heat BalanceWhen processing very light tight oil derived feedstocks, insufficientcatalytic activity requires that the catalyst circulation rate increaseso that conversion, and thus the coke yield from the catalyst,increases to satisfy the FCC heat balance. If the FCCU cannotphysically circulate enough catalyst, it will be necessary to eitherreduce the unit charge rate or the reaction severity to stay withinthe FCC catalyst circulation limit. Alternatively, refiners can satisfythe heat balance by blending in a heavier feedstock, recyclingslurry, burning torch oil, increasing regenerator air preheat, or
FIGURE 9: ACHIEVE™ Catalyst Delivers Superior Metals Tolerance Compared to a Competitive Base
Competitive Base
ACHIEVETM Catalyst
2.0
1.8
1.6
1.4
200
240
280
320
360
1.2
4
5
6
Ecat Ni Equivalents, ppm
2400 2550 2700 2850 3000
2400 2550 2700 2850 3000
Gas FactorCoke Factor
H2 Yield, SCFB
14 Issue No. 114 / 2014
derating the stripping steam. However, these options often have a
detrimental effect on the operation28,29. Table VIII 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.
As an example of the role of catalyst activity in maintaining heat
balance, consider an FCC unit operating on standard VGO that 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.
FIGURE 10: Unit Data Demonstrating Improved Performance of ACHIEVE™ Catalyst Versus the Competitive Base
2.0
0
-20
-40
-3.0
-1.5
0.0
1.5
3.0
CompetitiveBase
Hydrogen, SCFB Conversion, vol.% Gasoline, vol.%
Gasoline + LCO, vol.% Slurry, vol.% Delta Coke
CompetitiveBase
CompetitiveBase
ACHIEVETM
CatalystACHIEVETM
CatalystACHIEVETM
Catalyst
2
4
6
2
-2
0
-2
0
2
4
0.2
-2
0
-0.2
0.0
Operating Parameters Delta (ACHIEVE™-Competitive Base)
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
TABLE VII: ACHIEVE™ Yield Shifts Deliver$0.70/BBLBenefit
Grace Catalysts Technologies Catalagram® 15
FIGURE 11: C/O Ratio Must Increase to Satisfy Heat Balance, After Shift to Light Tight Oil
Coke, wt.% Conversion, wt.%
9.0
8.0
7.0
6.0
3.0
4.0
5.0
9.0
8.0
7.0
6.0
3.0
4.0
5.0
64.0 68.0 72.0 76.0 80.01.0 2.0 3.0
Base - VGO Feed Light Tight Oil Feed
Cat
-to-O
il R
atio
Option Potential Issues
Blend in heavier feedstock Availability of heavier feedstock. Crude incompatibility and asphaltene precipitation. High metals in heavier crudes.
Increase feed preheat Increased energy consumption. Metallurgical limits. Increase in non-selective thermal cracking and dry gas production.
Slurry recycle Feed system fouling. Catalyst erosion. Increased dry gas yield.
Burning torch oil in the regenerator Accelerated catalyst deactivation. Burning of a high value stream.
Reduce stripping steam rate Wear of stripper steam rings. Stripper steam plugging. Accelerated catalyst deactivation.
Increase preheat of regenerator air Increased catalyst and air grid nozzle attrition.
Increase FCC catalyst activity Best and most profitable option for maintaining heat balance.
TABLE VIII: Options for Maintaining Heat Balance with Light Feeds
16 Issue No. 114 / 2014
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. 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 IX. The feed was light and
paraffinic with an API of 29.5. Table X 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 XI 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.
Maintaining Refinery Pool OctaneA 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 XII, 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 in Table XIII.
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
FIGURE 12: Effect of Change in Catalyst Activity on Catalyst to Oil Requirements to Maintain Constant Coke
Coke, wt.% Conversion, wt.%
9.0
8.0
7.0
6.0
3.0
4.0
5.0
9.0
8.0
7.0
6.0
3.0
4.0
5.0
64.0 68.0 72.0 76.0 80.01.0 2.0 3.0
Base - VGO Feed Light Tight Oil Feed
Cat
-to-O
il R
atio
Catalyst A
Grace Catalysts Technologies Catalagram® 17
Feed PropertiesAPI Gravity, ˚F 29.5
CCR, wt.% 0.29
K-factor 12.19
n-d-m AnalysisCa, Aromatic Ring Carbons, % 13.9
Cn, Naphthenic Ring Carbons, % 16.9
Cp, Paraffinic Carbons, % 69.2
Equilibrium Catalyst Properties
TABLE IX: Feed and Catalyst Properties for Commercial Application of High Activity Catalyst with Light Feed
Competitive Base ACHIEVETM Catalyst
Zeolite Surface Area, m2/g 164 154
Ni, ppm 176 203
V, ppm 892 1022
Competitive Base
ACHIEVETM
CatalystC/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 C4's, 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
TABLE X: ACHIEVE™ Catalyst Outperforms Competitive Technology in a Light Feed Application - Yields at Constant Conversion
Competitive Base
ACHIEVETM
Catalyst
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 C4's, wt.% 12.7 12.9
Gasoline, wt.% 54.2 55.3
LCO, wt.% 17.2 16.9
Bottoms, wt.% 6.8 5.7
TABLE XI: ACHIEVE™ Catalyst Outperforms Competitive Technology in a Light Feed Application - Yields at Constant Coke
FIGURE 13: ACHIEVE™ 400 Catalyst Preferentially Cracks Gasoline Olefins at C7 and Above
Reactant SelectivityRelative
Selectivity C3=/C4=
C8=2 C4=C3= + C5=
44%56% 100 0.64
C7=C3= + C4=C2= + C5=
95%2% 12 1.0
C6=2 C3=C2= + C4=
83%16% 1.5 11
ACHEIVETM 400 Catalyst
ZSM-5 Additive
Buchanan, et. al., Ref. 30
18 Issue No. 114 / 2014
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.
Carbon Number
0 1 2 3 4 5 6 7
1.5
0.5
0
-0.5
-1
1
Base MIDAS® Catalyst + OlefinsMax® Additive ACHIEVETM 400 Catalyst
Ole
fins,
wt.%
FF
FIGURE 14: Incremental Olefin Yields by Carbon Number at Constant Conversion Demonstrate thatACHIEVE™ 400 Catalyst Does Not Crack C6 Olefins as ZSM-5 Based Additives Do
0.7 0.8 0.9 1 1.1 1.2 1.3 1.40.6
C3=
C4=
1.4
1
0.8
0.6
1.2
Base MIDAS® Catalyst + OlefinsMax® Additive ACHIEVETM 400 Catalyst
FIGURE 15: At Constant Conversion ACHIEVE™ 400Delivers a Higher Ratio of C4 to C3 Olefins than Use ofa Separate ZSM-5 Based Olefins Additive
94.6
93.8
93.4
93.0
94.2
94.0
93.6
93.2
94.4
80.6
79.8
79.4
79.0
80.2
80.0
79.6
79.2
80.4
70 72 74 76 78
70 72 74 76 78
Conversion, wt.%
Conversion, wt.%
MO
NR
ON
Base MIDAS® Catalyst + OlefinsMax® Additive
ACHIEVETM 400 Catalyst
Base MIDAS® Catalyst
FIGURE 16: ACHIEVE™ Delivers Higher RON and MON
Grace Catalysts Technologies Catalagram® 19
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 4531. 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, paraffins,
aromatic, etc.), the degree of branching within a molecule affects
10
6
6 6.5
8
7
55.5
9B
otto
ms,
wt.%
7.5 87.0
Coke, wt.%
Base MIDAS® Catalyst + OlefinsMax® Additive
ACHIEVETM 400 Catalyst
Base MIDAS® Catalyst
FIGURE 17: Coke to Bottoms is Maintained withACHIEVE™ 400 Catalyst
tC4=cC4= 1-C4=iC4=
Base MIDAS® Catalyst + OlefinsMax® Additive
ACHIEVETM 400 Catalyst
40%
0%
20%
10%
30%
% T
otal
C4=
FIGURE 18: Distribution of Butylene Isomers forACHIEVE™ 400 and Base Midas® + OlefinsMax®
Res
earc
h O
ctan
e N
umbe
rM
otor
Oct
ane
Num
ber
140
-20
60
20
100120
-40
40
0
80
-80-60
-20
60
20
100120
-40
40
0
80
-80-60
2 4 6 8 10 12 14
2 4 6 8 10 12 14
Aromatics Olefins Naphthalenes
monomethyl-iso-paraffins n-paraffins
Carbon Number
Carbon Number
FIGURE 19: Pure Component RON and MON as a Function of Hydrocarbon Type and Carbon Number(Based on API Research Project 45)
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 9731. The octane
enhancement from the ACHIEVE™ 400 catalyst is from increased
gasoline olefins and from increased olefins isomerization. In Table
XII, the PIANO data shows 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™
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 case where butylene is valued at
$45/bbl over gasoline, each 0.1 wt.% increase in butylene
selectivity results in >$0.8MM/yr more value.
20 Issue No. 114 / 2014
Base MIDAS® Catalyst
Base MIDAS® Catalyst+
OlefinsMax® Additive
ACHIEVETM 400 Catalyst
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 C4's, 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
C4=/C3=, wt.% -- 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
TABLE XII: ACHIEVE™ 400 Catalyst Provides Higher Octane and More C4 Olefins than Using ZSM-5 Additive
Base MIDAS® Catalyst
Base MIDAS® Catalyst+
OlefinsMax® Additive
ACHIEVETM 400 Catalyst
Al2O3, % 55.9 55.3 54.5
RE2O3, % 1.4 1.4 1.4
ABD, g/cm3 0.70 0.67 0.70
APS, microns 78 76 75
ZSA, m2/g 134 140 145
MSA, m2/g 140 142 143
TABLE XIII: Fresh Catalyst Properties
ConclusionThe 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 most 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 allows opportunity to
optimize the operating parameters and catalyst management
strategies, enabling a more stable and profitable operation.
Grace Catalysts Technologies Catalagram® 21
AcknowledgementsThe authors thank colleagues at Grace for assistance with the
testing and analysis for this paper. The many contributions of
Olivia Topete and Jeff Koebel to this paper are gratefully
acknowledged.
References1. 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.
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.
Base MIDAS® Catalyst + OlefinsMax® Additive
ACHIEVETM 400 Catalyst
Base MIDAS® Catalyst
0.63
0.6
0.57
0.55
0.61
94.0
0.58
0.56
0.62
0.52
0.48
0.46
0.44
0.5
0.49
0.47
0.45
0.51
0.42
0.43
70 72 74 76 78Conversion, wt.%
70 72 74 76 78Conversion, wt.%
C5=
Bra
nche
d/C
5 Tot
alC
6= B
ranc
hed/
C6 T
otal
FIGURE 20: ACHIEVE™ 400 Catalyst Results in Increased C5 and C6 Olefins Branching
FIGURE 21: Annualized Value of Improved ButyleneSelectivity for a 50,000 BBL/day FCCU
0 0.1 0.2 0.3 0.4 0.5 0.6
$45/BBL
Uplift from Gasoline to C4= (%)
$6,000,000
$5,000,000
$4,000,000
$3,000,000
$2,000,000
$1,000,000
Value Differentialbetween C4= andGasoline
$60/BBL
$15/BBL$30/BBL
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.
22 Issue No. 114 / 2014
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.
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 Catalysts Technologies Catalagram® 23
Tight Oil Distillate in ULSD Production, What To Expect?
Greg RosinskiHydrotreating TechnicalService Engineer
Brian WatkinsManager,Hydrotreating PilotPlant and TechnicalService Engineer
Charles OlsenDirector, Distillate R&Dand Technical Service
Advanced Refining TechnologiesChicago, IL, USA
Global growth in distillate demand has driven refiners to maximize their middle distillate yield while trying
to manage final product properties such as cold flow properties, color, and cetane. This has been coupled
with the availability of new domestic and unconventional crude oil sources and the global disparity in
hydrogen cost and availability. This has given some refiners a unique opportunity to exploit different
catalytic routes to maximizing middle distillate production. Catalytic solutions to increase middle distillate
yield while controlling final product properties include hydrotreating, hydrocracking, and hydrodewaxing.
Each of these routes present challenges in terms of hydrogen consumption, yield shifts, changes in cycle
life, and the chemistry involved.
In addition to new sources of crude, the price of natural gas in the North America has decreased and is
significantly lower than the rest of the world (Figure 1). This has given North American refiners an
incentive to pursue volume gain due to the reduced cost of hydrogen derived from natural gas.
Furthermore, worldwide demand for distillates has grown, and the U.S., while still a net importer of crude
oil, has become a net exporter of refined products due in part to a competitive cost advantage in
hydrogen (Figure 2). ULSD comprises the largest amount of net exports, with most of the balance being
gasoline and jet fuel. Thus, U.S. Refiners have been utilizing their competitive advantage in fuels
production as the relative price of natural gas has fallen.
In the last decade new sources of crude have also come on the market (Figure 3). Most of the increase
has come from bitumen derived synthetic crudes from Canada or more recently from shale oil formations,
principally Bakken and Eagle Ford. Since 2007 almost one million barrels of new synthetic crude from
Canada has become available and shale formations have provided over two million barrels of additional
crude to the North American market. Almost all of the new crude to come to market is captive to North
America. Refiners have eagerly tried to utilize these new sources of crude due to pricing and availability,
which has lead to enhanced profitability for refiners who have access to these new crude sources.
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