Light Olefin Technologies

Bryan Glover
UOP LLC

Journées Annuelles du Pétrole

October 11, 2007
2006 UOP LLC. All rights reserved.
© 2007 UOP 4867-01
UOP 4638-01
Light Olefin Technologies
Alternatives to Thermal Cracking for the production
of light olefins:
• Propane dehydrogenation to Propylene
- Oleflex process
• Olefin Conversion Processes
- Metathesis
- Olefin Cracking
• Methanol to Olefins
- SAPO-34 and ZSM-5 based systems
• High Severity FCC processes
- PetroFCC
• Naphtha cracker feed enrichment
- MaxEne Process for separation of normal
paraffins from naphtha for increased
naphtha cracker ethylene yield
UOP 4867-02
 Relative Light Olefin Yields

MTO
MTO ++ OC
OC
Issues to Consider
MTO
MTO
• Feed availability
Propane
Propane Dehydro
Dehydro and price
PetroFCC
PetroFCC ++ ARU
ARU +OC
+OC • Relative Capex
FCC
FCC • Multi product slate
/ integration
Nap.
Nap. Cracking
Cracking ++ OC
OC

Naphtha
Naphtha Cracking
Cracking

0%
0% 20%
20% 40%
40% 60%
60% 80%
80% 100%
100%
Product
Product Mix
Mix
Propylene
Propylene Ethylene
Ethylene BTX
BTX
Butadiene
Butadiene Mixed
Mixed C4s
C4s Gasoline
Gasoline
Cycle
Cycle Oil
Oil Slurry Oil
Slurry Oil Light
Light Ends
Ends

UOP 4867-03
Propane Dehydrogenation

• On-purpose production of propylene

from propane
• Produces propylene and hydrogen
• Typically Pt or Cr based systems

Catalyst
Propane Propylene &
Hydrogen
-ΔT
C3H8 C3H6 & H2

UOP 4867-04
Propane Dehydrogenation
The Oleflex Process

1.2 MT Propane

1.0 MT Propylene

VC + FC Inputs

Utilities
Catalyst
Chemicals
Labor, etc.

High yield Pt based catalyst

UOP 4867-05
Propane Dehydrogenation
The Oleflex Process

Net Gas C2-

H2
Deethanizer
Propylene
Oleflex SHP
P-P Splitter

Depropanizer
C3 LPG

C4+

UOP 4867-06
Propane Dehydrogenation
The Oleflex Process
Reactor Regeneration
Section Section

C
C Product Recovery Section
R
Turbo
Expander
Dryer
Rx Effluent
Compressor
Heater Cells

To SHP
H2 Recycle

Fresh Net
& Recycle Separator
Feed Off Gas

UOP 4867-07
Olefin Conversion Processes

Two types: Metathesis & Olefin Cracking

Catalyst
Ethylene &
Metathesis Propylene
2-Butene
C3H6
C2H4 & C4H8
(plus by-products)

Catalyst
C4 to C8 Ethylene &
Olefins Olefin Cracking Propylene
C4H8 to C8H16
- ΔT
C2H4 & C3H6
(plus by-products)

UOP 4867-08
 Olefin Cracking
TOTAL PETROCHEMICALS / UOP Olefin Cracking Process

Light
Olefin
Olefinic Product
C4 - C 8
Feed Depropanizer
SHP Column
OC
Reactor C4 & C5
Purge

Recycle Rerun
Column

C6+
Purge
UOP 4867-09
Olefin Cracking
The Mechanism

Feed Cracking Product

Olefins Olefins

Aromatics &
Oligomers Hydride Coke
Paraffins/H2
transfer

• C4= do not crack directly

• In principle, it is possible to produce Propylene and
higher olefins from Ethylene
- Ethylene activation is facilitated in the presence of
higher olefin

UOP 4867-10
TOTAL PETROCHEMICALS / UOP
Olefin Cracking Process

• 80% to 90% overall conversion Olefin Cracking

of higher olefins Light Olefin Product
• High selectivity to light olefins
C4+
C4+
- 3.5 to 4.0 propylene/ethylene C1-
C1-
Propane
Propane
product ratio Ethene
Ethene
• Over 90% olefin purity in C2 & C3
fractions
- Upgrading to polymer grade is simple Ethane
Ethane

• Fixed-bed technology
- Swing regeneration system
- High LHSV
- Low Rx pressure (between 1 and 5 bar)
• Reactor inlet temperatures 500 to 600°C Propene
Propene

• No diluent addition

UOP 4867-11
 Olefin Cracking Process
Applications

Naphtha
C 2= C 2=
Product C 3= MTO
Furnace Recovery
Product& MeOH
Furnace Fuel Gas C 3=
Purification&
Recovery
Pygas
Refineries C4-C5
Light
Gas Olefins
Light Gasoline Olefins
Oils
C4/C5 Olefins FCC Cycle Oils
FCC
Olefin C 2=
C5/C6 Cracking C 3= Olefin
C 4+
Paraffin-Rich Cracking
Olefin
C4-C8
Naphtha Crackers Recovery
Olefin
MTO Plants
LPG
Olefin
Cracking Light
Olefins

Olefin Cracking can be integrated with a variety

of other processes
UOP 4867-12
Methanol to Olefins

Gas to Olefins (GTO)

Natural Gas

Synthesis Ethylene &

Gas
Production
Methanol
Methanol
Synthesis MTO Propylene

Coal

Coal to Olefins (CTO)

UOP 4867-13
Methanol to Olefins
ZSM-5

ZSM-5 (MFI)

y Mobil discovered ZSM-5

5.6 x 5.3
for methanol to gasoline
(MTG) and olefins during
10R 10R early 1970s

y MTG commercialized in
New Zealand during mid
1980s.

Medium pore size: 5.1 x 5.5Å

UOP 4867-14
 Methanol to Olefins
SAPO-34

SAPO-34

y Silicoalumino-Phosphates
(SAPO) discovered in the
early 1980s by scientists at
Union Carbide (UCC)
y SAPO-34 has high
selectivity for MTO
reaction.
3.8A
y MTO development
8-ring
transferred from UCC to
UOP in 1988

L. Smith et al, Catal. Lett. 1996, 41, 13

UOP 4867-15
Methanol to Olefins
SAPO-34 Comparison to ZSM-5

3.8 Ă 5.5 Ă

Small Pore Medium Pore

Weak Acid Strong Acid
Sites Sites
UOP 4867-16
 Methanol to Olefins
Once Through Yields SAPO-34 and ZSM-5

70 SAPO-34 ZSM-5
Type Type
60 Ethylene 31 6

50 Propylene 47 42

Light Olefins 78 48
40
% Yield

30

20

10 • SAPO-34 has slightly higher

coke selectivity
0
C2= C3= C4= C5+ C1-C5 Coke+
Paraffins COx

• C4+ olefin conversion could

• SAPO-34 produces more improve light olefin yields
light olefins UOP 4867-17
 Methanol to Olefins
Yields with C4+ Olefin Recycle
SAPO-34 ZSM-5
70 Type Type
Ethylene 29 nil
60
Propylene 60 65
50
Light Olefins 89 65
40
% Yield

30 MeOH 2.6 3.5

Consumption,
kg/kg Olefin
20

10 Low methanol consumption

0
C2= C3= C4= C5+ C1-C5 Coke+
Paraffins COx

• C4+ from SAPO almost entirely converted

• C4+ from ZSM-5 higher in aromatics
UOP 4867-18
Methanol to Olefins
UOP/HYDRO MTO Process
Quench Caustic C2 C3
Reactor Regenerator tower Scrubber wash De-
De-C2 De-
De-C1 splitter De-
De-C3 splitter De-
De-C4
Tail gas

Ethylene
Regen gas
Propylene
Dryer
Mixed C4

DME &
Oxygen.
Recovery C2H2
reactor

C5+
Air Water
Propane
Water
Ethane
Methanol

y Fluidized bed reactor & regenerator with continuous

steady state operation and polymer-grade ethylene
and propylene product
UOP 4867-19
Methanol to Olefins
C4+ Olefin Conversion

• Heavies can be converted

using UOP/Total C2=
Petrochemicals Olefin MeOH MTO
C3=
Cracking Process (OCP)
• Zeolite based system is C4-C5 Light
needed for heavies Olefins Olefins

conversion – higher
acidity, larger pore size.
Olefin C4+
Cracking

UOP 4867-20
Methanol to Olefins
Expanded P/E Ratio of Advanced MTO

• Increased propylene production thanks to:

- Catalyst improvements
- Process optimization
100
Ethylene + Propylene, wt%

90
(C Basis)

80 P/E up to 2.1
with high selectivity

70

60
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
P/E Ratios - Products
UOP 4867-21
FCC Unit Design & Operating Envelopes

PetroFCC
Technology
Propylene Yield, wt-%FF

Gasoline Yield, wt-% FF

60

20

10 30

5
f (Rx T, PP, C/O, PT)
Maximum Gasoline Maximum
Gasoline + LPG Propylene
UOP 4867-22
The PetroFCC Process
TM

Ethylene y High cat / oil

Propylene – RxCat technology:
– De-couples catalyst
Mixed C4s circulation from heat
Aromatic balance
naphtha y Low partial pressure
Cycle oils – Optimize Steam and
Operating Pressure
y Optimized Catalyst
Selection
y High Temperature
RxCat™ y Increased flexibility
Technology UOP 4867-23
Naphtha Cracker Feed Enrichment
The MaxEne Process

• Adsorptive separation system for extraction of

normal paraffins from naphtha
- Full range naphtha (C6 to C12)
- Extract
Š High recovery of normal paraffins
Š Normal paraffin purity up to 95%
Š Liquid phase, low temperature and pressure
Š Low utilities Naphtha
- Raffinate Cracker

Š Superior catalytic reformer feed

C7-
MaxEne
Full Range Naphtha Unit

Catalytic
Reformer

C7+
UOP 4867-24
 Naphtha Cracker Feed Enrichment
The MaxEne Process

Adsorptive separation
• The adsorbent has greater
Adsorbent affinity for n-paraffins
chamber 1
Extract
Rotary column Simulates a moving bed
De

valve
so

• The process influent and

rb

2 n-Paraffins
en

feed to
effluent points move, but
t

3
4 Desorbent steam
5
Extrac
t cracker
the actual mechanical
6 Feed
7
connections do not
8 Raffinat
e
• The solid adsorbent is in
Raffinate packed, non-moving beds
column
• The liquid feed flows counter-
Pumparound
Naphtha
Feed to currently relative to the solid
pump reformer

UOP 4867-25
The MaxEne Process Effect
Single-pass Steam Cracker Yields

40
Cracker effluent, wt-%

Typical Complex
30 With a MaxEne Unit

20

10

ne
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dr o

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Py

Et

Et h
op
Me

Be
Pr

Bu
Hy

Pr
UOP 4867-26
Conclusions

• New routes must be considered to meet future

ethylene and propylene demand
• A range of economically attractive options are
available to meet this demand
• Each producer must consider key selection factors
- Feedstock availability
- Desired product slate
- Integration with existing facilities

UOP 4867-27
UOP 4867-28