processing tight oils in fcc: issues, opportunities and ... · grace catalysts technologies...

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)


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


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


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


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


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


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


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


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


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


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


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


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.%




FIGURE 17: Coke to Bottoms is Maintained withACHIEVE™ 400 Catalyst

tC4=cC4= 1-C4=iC4=



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+

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 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+

OlefinsMax® Additive


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.


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.




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

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“Gasoline Quality- The Measurement of Compositions and

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22. Ritter, R.E., “Light Cycle Oil from the FCC Unit AM-88-57,”

1988 NPRA Annual Meeting, San Antonio, Texas.

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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.

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Oils in FCC: Challenges and Opportunities,” Hydrocarbon

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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.

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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.

processing tight oils in fcc: issues, opportunities and ... · grace catalysts technologies...

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