On-Purpose Propylene Technology Developments

Tim Foley UOP LLC

2005 UOP LLC. All rights reserved.

UOP 4288K-1

On-Purpose Propylene:
Propylene supply/demand overview Alternatives to steam cracking for propylene production Refinery FCC Propane Dehydrogenation Methanol to Olefins Olefin Conversion Selection of a propylene process

C3H6

UOP 4288K-2

C3=/C2= Ratios
Worldwide
0.45 0.64
MT Propylene / MT Ethylene

Steam Cracker Production

0.62
Demand ~ 18 M MTA
Sup ply from stea m cr acke rs

0.40

0.36 0.54 2014

0.35 2004

2006

2008

2010

2012

Year
Data Source: CMAI 2005
UOP 4399A-4

Demand

0.59

Propylene Supply & Demand

Polymer Grade & Chemical Grade
100 Million MTA
se po r Pu

2004 Supply
Steam Cracker
~ 67%

90 80 70
ta To

d On n er ma th e O lD Refinery

Steam Crackers

Dehydro Others

Current Capacity 60 2004 2006 2008 2010 2012 2014 Year

Substantially more propylene will have Substantially more propylene will have to come from on-purpose technologies to come from on-purpose technologies

UOP 4399A-2

Source: CMAI

38%

Refinery

On-Purpose Propylene Technologies

VGO, ATM Resid Propane

High-Severity FCC High-Severity TM PetroFCCTM Process

TM OleflexTM Process

MTO

Olefin Cracking

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-5

On-Purpose Propylene Technologies

VGO, ATM Resid Propane

High-Severity FCC High-Severity TM PetroFCCTM Process

TM OleflexTM Process

MTO

Olefin Cracking

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-6

Propylene from Refineries

Crude Column C4 and Lighter Straight Run Gasoline Kerosene AGO Crude Oil Downstream Processing
Gasoline Diesel

PRU

Propylene Fuel Gas LPG

FCC
VGO

Vacuum Column Vacuum Residue

Heavy Fuel Oil

UOP 4288K-4

Propylene from FCC

tion duc Pro lene opy High-Severity g Pr n
Enhanced Propylene 5 7 wt% C3= Gasoline FCC 10 -16 wt% C2= C3= Gasoline

Propylene Yield

PetroFCC 20 + wt% C2= C3= Aromatics

easi Incr

Max. Gasoline 3 - 5 wt% Gasoline

Unit Design and Operation

UOP 4399A-7

High Severity FCC

A Flexible Process
Steps to increase propylene Increase riser temperature Use low H-transfer catalyst Use shape selective additive Use new reactor technology
RxCatTM

Designed with the flexibility to operate Designed with the flexibility to operate in aapropylene or gasoline mode in propylene or gasoline mode
UOP 4399A-8

What is the PetroFCC Process?

RxCat and PetroFCC Benefits:
Enhanced catalytic cracking Increased propylene yield Reduced thermal cracking Decreased dry gas yield Catalyst selection flexibility Choice of catalyst supply
Optimized for feedstock and product objectives RxCat Technology
UOP 4399A-11

Typical PetroFCC Process Yield, wt-%

(VGO Feed)
Traditional FCC PetroFCC Process C2=
9

Light Olefins 6 22

3 6.5 11

C2C3s C4s

C3=
24

C4=
53.5 19

14

Naphtha
28 14 7 5

Aromatics
BTX 18

Distillate Fuel Oil Coke

9.5 5 5.5

UOP 4399A-12

Is Integration an Objective?
Other Feeds
Olefin OCP Cracking Olefins Recovery

Gas Con

Light gases Ethylene Propylene Mixed C4s

Gas Oil

Aromatic Naphtha
SulfolaneTM Process SulfolaneTM Process Fractionation Fractionation Process Process TatorayTM TatorayTM Process Process IsomarTM IsomarTM Process Process

ParexTM ParexTM Process Process

Benzene p-Xylene

UOP 4399A-27

On-Purpose Propylene Technologies

VGO, ATM Resid Propane

High-Severity FCC PetroFCCTM Process

OleflexTM Process

MTO

Olefin Cracking

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-13

What is Propane Dehydrogenation (PDH)?

On-purpose production of propylene from propane Produces propylene and hydrogen
Catalyst

Propane
T
C3H8

Propylene & Hydrogen

C3H6 & H2

UOP 4354J-12

C3 Oleflex Process
Net Gas Propane H2 C2 Deethanizer

Propylene

Oleflex

SHP

Propane Feed

C4+

Six operating units with capacities ranging from 100,000 to 350,000 MTA propylene 1.25 M MTA operating capacity 40 plus plant years of operating experience Larger unit capacities in design
UOP 4399A-15

Depropanizer

P - P Splitter

On-Purpose Propylene Technologies

VGO, ATM Resid Propane

High-Severity FCC PetroFCCTM Process

OleflexTM Process

MTO

Olefin Cracking

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-16

What is MTO?
Gas to Olefins (GTO)
Natural Gas

Synthesis Gas Production

Methanol Methanol Synthesis

MTO

Ethylene & Propylene

Coal

Coal to Olefins (CTO)

UOP 4399A-17

UOP/HYDRO MTO Process

Reactor Regenerator Quench Tower
Regen Gas

High selectivity to light olefins

Ethylene & Propylene

Oxygenate Recovery

Light Olefin Recovery

Minimizes feedstock costs High value product mix with little C5+ co-product Little hydrogen & methane

Air

Water

Flexibility of C2=/C3= product ratios

Water

Methanol
UOP 4399a-18

Why MTO?
100% 80% 60% 40% 20%
Naphtha Cracker MTO
ge nta a Adv O MT

Product values generally increase with crude oil prices Naphtha cracker feedstock prices are closely linked to crude oil prices
High feedstock costs offset most of the economic benefits as product values increase

ROI

MTO feedstock is from dedicated sources using cost advantaged feedstock

Fixed price not tied to crude oil Can support increased methanol prices when olefin values are higher (high crude oil prices) MTO is competitive with steam crackers when crude oil is above $16 per barrel
Huge advantage when crude oil prices are high
UOP 4399A-19

0% 10 20 30 40 50 Crude Oil Benchmark, $/BBL

On-Purpose Propylene Technologies

VGO, ATM Resid Propane

High-Severity FCC PetroFCCTM Process

OleflexTM Process

MTO

Olefin Cracking

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-20

What is Olefin Cracking?

Production of propylene and ethylene from C4 to C8 olefins
C4 to C8 Olefins
C4H8 to C8H16

Catalyst

Olefin Cracking
T

Ethylene & Propylene

C2H4 & C3H6

UOP 4399A-21

ATOFINA/UOP Olefin Cracking Process

Naphtha
Product Recovery & Product Purification Recovery &

Applications
C2= C3= Fuel Gas Pygas Gas Oils MeOH

MTO

C2= C3= Light Olefins

Furnace Furnace

Refineries
FCC
Gasoline Cycle Oils C2= C3=

C4-C5 Olefins

C4/C5 C5/C6 Paraffin-Rich

Light Olefins

FCC

Olefin Cracking
C4-C8

Olefin Cracking

C4+

Naphtha Crackers

Olefin Olefin Recovery

LPG Light Olefins

MTO Plants

Olefin Cracking

UOP 4399A-22

Olefin Cracking can be integrated Olefin Cracking can be integrated with aavariety of processes with variety of processes

Selection of Propylene Options

Key Issues
Feedstock
Cost Flexibility

Yields
Co-products Integration

Capacity
Incremental New complex

Capital

UOP 4399A-23

What Products are Desired?

MTO + OC MTO + OC MTO MTO Propane Dehydro Propane Dehydro PetroFCC + ARU +OC PetroFCC + ARU +OC FCC FCC Nap. Cracking + OC Nap. Cracking + OC Naphtha Cracking Naphtha Cracking 0% 0% 20% 20% 40% 40% 60% 60% 80% 100% 80% 100%

Issues to Consider Propylene yield Co-products Integration

Product Mix Product Mix

Propylene Propylene Gasoline Gasoline Ethylene Ethylene Cycle Oil Cycle Oil BTX BTX Slurry Oil Slurry Oil Butadiene Butadiene Light Ends Light Ends Mixed C4s Mixed C4s

UOP 4399A-24

How Much Propylene Is Desired?

Propylene Capacity, kMTA 600 500 400 300 200 100 0
Cracker Furnaces FCC revamp PRU Oleflex Olefin Cracking MTO High Severity FCC Naphtha Cracker Oleflex MTO PetroFCC Olefin Cracking

Incremental (<200 kMTA)

Revamp existing assets

Intermediate (100 300 kMTA)

Integrate new units with existing assets

World scale (>250 kMTA) New Unit Grass Roots Integrations

New complexes Integration

Revamps

UOP 4399A-25

How Much Capital is Available?

MTO / GTO Olefin Cracking Propane Dehydro. FCC PRU Add. FCC/PetroFCC Naphtha Cracker 0 200 400 600 800 1000
BTX MeOH

Low capital (<$200 M)

FCC PRU FCC Revamp OC

Intermediate capital (<$500 M)

Oleflex PetroFCC MTO

Large capital (>$500 M)

GTO PetroFCC/ARU/OC Millions US$

Excludes Olefin Derivative Units

UOP 4399A-26

On-Purpose Propylene Technologies

Summary
VGO, ATM Resid High-Severity FCC & PetroFCC Process
Proximity to C3= users C3= & gasoline flexibility Refinery / PC integration

Propane OleflexTM Process

Propylene/Propane price differential Simple back-integration one feed one product

MTO
Monetize natural gas or coal High yields of C3= & C2= Competitive with steam cracking

Olefin Cracking
Feedstock flexibility Integration flexibility Economic over a broad range of C3= / C2= prices

Natural Gas, Coal, Methanol

Mixed C4= to C8=

UOP 4399A-28

Conclusions
New options must be considered to meet future propylene demand Several options available for increasing propylene Each producer must consider key selection factors UOP can help!

UOP 4399A-29

Acknowledgments: Bipin Vora, Mark Houdek, Chuck Hemler, Bob James, Joe Gregor, Jim Andersen UOP Henning R Nilsen, Steinar Kvisle Norsk Hydro Walter Vermieren Total Petrochemicals
UOP 4288K-27