Solutions for Maximizing Value with

FCC Feeds from Opportunity Crudes

Alexis Shackleford

RefComm GalvestonMay 4-8 2015

BASF Refining Catalysts

2

What is Tight Oil?

� Tight Oil: oil produced from low permeability (e.g. tight) shale,

sandstone and carbonate rock formations

� Game-changer for North American refining industry

Sources: EIA (US Energy Information Administration)

3

Tight Oil Quality Variability from One Field Source Baker Hughes

Bitumen Recovery from Oil Sands: Properties will Differ Based on Upgrading

Shovel & Truck

Extraction /

Flotation

SAGD*

Diluted

Bitumen

(DilBit)

Oil Sand Synthetic

Crude Oil

(SCO)30% In-Situ

70% Mining

UP

GR

AD

ER

*Steam Assisted Gravity Drainage

FCC Feed VGO Cut Properties

� Tight Oil

� Highly paraffinic

� Very low Sulfur

� Low Ni and V

� Low coke producing feed

5

VGO Cut Property TX Shale

BakkenCore WTI

Maya Blend Wabasca

Cold Lake

API Gravity 31.9 24.5 26.3 21 13.4 14.9

Sulfur wt% 0.18 0.27 0.46 2.05 4.31 3.56

Nickel ppm 0.09 0.47 0 0.64 3.79 1.8

Vanadium ppm 0.08 0.14 0 4.48 5.1 5.18

Con Carbon wt% 0.03 0.68 0.01 0.47 1.41 1.69

Source: KBC. Coking and CatCracking Conference by The Refining Community, Galveston TX. May

6-10 2013

� Oils Sands

� Aromatic feeds

� High Sulfur

� High Ni and V

� High Con Carbon

FCC Operation with Tight Oil

� Less VGO available

� Wet gas handling limit

� Heat balance concerns

� Max Feed Preheat, feed resid and/or use heavy recycle

� Low gasoline pool octane

� Low REO catalyst and/or use ZSM-5

� Low Sulfur, Nickel and Vanadium

� Higher alkali and iron contaminant

6

FCC Operation with Oil Sands

� Operations depends on how much upgrading was done before

� Lower conversion

� Ensure proper feed vaporization

� Higher cat deactivation: change cat make-up strategy

� Higher delta coke

� Requires higher air rate – Don’t exceed cyclone superficial velocity resulting in high cat

losses!

� Manage high regenerator temperature

� High Sulfur and nitrogen: manage gasoline specifications and emissions

� High Nickel and Vanadium – change catalyst technology

7

Feedstock CharacterizationThree Hydrotreated Bitumen vs. reference VGO

� Even after severe hydrotreating bitumen derived feeds maintain high aromatic content

� High percentage of mono and di aromatics indicate high conversion possible

Feeds Reference A B C

API 22.5 21.5 22.5 25.4

Sulfur 0.8 0.2 0.2 0.1

Hydrocarbon Type by SARA & GC-MS

Saturates 73 44 43 60

Aromatics:

Mono 7 32 33 25

Di 4 10 10 7

Tri+ / Polars 16 14 14 8

Most Severe Hydrotreating (Feed C) is required to match VGO feed reactivity

BASF ACE at 990 deg-F RxT

Base Catalyst

69

70

71

72

73

74

75

76

77

78

3 5 7 9 11

43

0 F

Co

nve

rsio

n,

wt%

Cat/Oil Ratio

Reference: API 22.5

Feed A: API 21.5

Feed B: API 22.5

Feed C: API 25.5

Iron in Feed

� High Iron in feed results in:

� Mild dehydrogenation catalyst that increases coke and hydrogen yields

� Mild CO promotion

� Plugging of catalyst pores by “iron nodules” at very high Fe content

10ECat from a unit processing Tight Oil, Fe = 1.5 wt%

“Iron Nodules”

High Iron on ECat

� High porosity

catalyst such as

BASF’s DMS

and Prox-SMZ

have very high

tolerance to iron

pore mouth

plugging

� One unit

successfully ran

above 2 wt%

����

Other Suppliers

BASF Users

11

� Many FCCs already process “dumbbell” type feeds via blending

hydrocracker bottoms with VGO or resid

� Feed compatibility needs to be considered due to asphaltene precipitation

mainly in the feed system

� Number of methods available for feed compatibility testing

� Main concern is with modeling these feeds, need to model them as separate

feeds vs. average properties

12

Dumbbell Feeds

Adapting to the Changing Market Place: Impact on FCC Operations and Catalysts 13

BASF Customer Not Processing Either

BASF Customer Processing Tight Oil

BASF Customer Processing Oil Sands

Opportunity Crudes heavily changing

North America

75%0%

62%77%

61%0%

67% 33%13%

13%

CANADA

http://religionanddiversity.ca

0%86%

Case #1: VGO FCC Processing Tight Oil

� Gulf Coast unit running 100% Eagle Ford

� Catalyst: NaphthaMax®

� API gravity increased from 22 to 28

� The lower feed N reduced NOxemissions

Case #1: VGO FCC Processing Tight Oil

� Ni and V

decreased

� Na and Fe

increased

15

Case #1: VGO FCC Processing Tight Oil

� To maintain regenerator bed temp, slurry recycle was increased to 15%

� No issue with catalyst circulation limit

16

� Conversion increased from 75 vol% to 86 vol% going to 100% tight oil

17

Case #1: VGO FCC Processing Tight Oil

Case #1: VGO FCC Processing Tight Oil

� Gasoline increases, then enters into the overcracking regime

� The gasoline RON decreases as the feed is more paraffinic

18

Case #1: VGO FCC Processing Tight Oil

� Total LPG increased from 24 vol% to 30 vol%

� This large increase in LPG may constrain the gas plant

19

Case #2:HT VGO FCC Processing Tight Oil

� This refinery process VGO, ~70%

of which is hydrotreated

� Went to 80% Eagle Ford

� Using BASF’s NaphthaMax® II

catalyst

� Since it is hydrotreated, properties

are similar

� No major unit operating

changes

� Limited by minimum regen

temperature

Operation Base Change

Feed Gravity API 26.6 +0.7

Feed Sulfur wt% 0.5 +0.1

Feed Nitrogen ppmw 960 -90

Feed Concarbon wt% 0.16 -

Preheat Temperature °F Base +43

Reactor Temperature °F Base +3

Dense Temperature °F Base +3

Catalyst Addition tons/day Base -

ZSM-5 Additions Yes (5%) No

Equilibrium Catalyst

ECat FACT wt% 77 -

Ni + V ppm 1500 +50

20

Case #2:HT VGO FCC Processing Tight Oil

� Conversion increased

� Lower dry gas and coke

� Despite ZSM-5 being removed,

the C3= make and total LPG is

higher

� Higher total liquid yield

� Unit is operating very well with

NaphthaMax® II catalyst with no

need to make a catalyst change

Normalized Yields Base Change

Conversion vol% 80 +2.0

Dry Gas wt% 1.8 -0.1

C3= vol% 8.4 +0.4

LPG vol% 27.7 +0.9

Gasoline vol% 63.6 +1.9

LCO vol% 15.3 -1.7

Slurry vol% 4.8 -0.3

Coke wt% 4.10 -0.05

Total Liquid Yield vol% 111.3 +0.9

21

Case #3:Mild Resid FCC Processing Tight Oil

� Prior to the introduction of Bakken, the

FCC ran VGO

� Due to the lack of VGO in Bakken, the

unit started processing reside for

improved economics

� Changed catalyst from BASFs

NaphthaMax® to Fortress™ for excellent

metals tolerance

22

Case #3:Mild Resid FCC Processing Tight Oil

� All contaminant

levels have

increased

� Conversion

dropped due to

heavier

feedstock

� The excellent

metal tolerance

of Fortress™

enabled a high

resid run

0

1000

2000

3000

4000N

i, V

(ppm

)

ECat Nickel and Vanadium

Ni V

0

0.2

0.4

0.6

0.8

Na (

wt%

)

ECat Sodium

0.55

0.65

0.75

0.85

0.95

1.05

1.15

Fe (

wt%

)

ECat Iron

0

1000

2000

3000

4000

Ca (

ppm

)

ECat Calcium

23

� FCC transitioned to process 25%

Syn Crude that is highly upgraded

� Use NaphthaMax II catalyst

� 90% of the feed is hydrotreated

� API Gravity increased 5.7 numbers

� Yet conversion only increased 3

numbers, with the majority of the

conversion coming from LCO

� Gasoline sulfur increased

24

Case #4HT VGO FCC Processing Oil Sands

Operation Base Change

Feed Gravity API 26.7 +5.7

Feed Sulfur wt% 0.09 +.04

Reactor Temperature °F 970 +17

Regen Bed Temp °F 1290 -

Slurry Recycle %FF 27% +7%

Equilibrium Catalyst

Activity % 75 -

Nickel + Vanadium ppm 1100 -

Normalized Yields

Conversion vol% 76.5 +3.0

LCO vol% 16.5 -2.2

Slurry vol% 7 -0.8

Product Properties

Hvy Gasoline Sulfur ppm 60 +40

Benchmarking Operations

50

55

60

65

70

75

80

85

90

95

17 19 21 23 25 27 29 31 33 35

Co

nvers

ion

, vo

l%

Feed Gravity, API

Conversion vs. Feed Gravity

Case 1: LTO VGOCase 2: LTO HT VGOCase 3: LTO Mild ResidCase 4: Oil Sands HT VGO

25

26

Wide Variety of Catalysts Used for Tight Oil & Oil Sands Operation

Gas Oil Max Conversion

- NaphthaMax®

- NaphthaMax® II

- NaphthaMax® III

- PetroMax™

- BituPro™

Gasoil Max Distillate Units

- HDXtra™

Resid Max Conversion Units

- Endurance®

- Flex-Tec®

- Fortress™

Resid Max Distillate Units

- Stamina™

Optimizing Value

Assuming Tight Oil feed and typical Gulf Coast Economics

� Maximize Conversion over LCO

� Maximize LPG= selectivity

� Increase Gasoline Octane

� Maximize Preheat

� Catalyst Management: More proactive catalyst management due to the

variability of the feed

� Contaminants Management

27

Summary

� Advantaged crude production will continue to

rise

� FCC catalyst technology and service must be

flexible to meet the changing feed quality and

operating conditions associated with the

crude

� There is no universal catalyst solution

� BASF is the market leader for tight oil FCC

applications providing catalyst solutions to

meet the unique challenges

28

29

30

Trademarks

Aegis, BituPro, Defender, Flex-Tec, Fortress, HDUltra, HDXtra, NaphthaMax and Stamina are

trademarks of BASF.

Although all statements and information in this publication are believed to be accurate and

reliable, they are presented gratis and for guidance only, and risks and liability for results

obtained by use of the products or application of the suggestions described are assumed by the

user. NO WARRANTIES OF ANY KIND, EITHER EXPRESS OR IMPLIED, INCLUDING

WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, ARE

MADE REGARDING PRODUCTS DESCRIBED OR DESIGNS, DATA OR INFORMATION SET

FORTH. Statements or suggestions concerning possible use of the products are made without

representation or warranty that any such use is free of patent infringement and are not

recommendations to infringe any patent. The user should not assume that toxicity data and

safety measures are indicated or that other measures may not be required.

© 2014 BASF