Converting Methanol to Propylene
(MTP)
M. Daftari
Gh. Joukar; NPC-RT General Manager
S. Sahebdelfar; Head of NPC-RT Catalyst Group
A. Firouzi; Head of NPC-RT Process Group
M. Asadi; NPC-RT Catalyst Group
H. Alaiee; NPC-RT Engineering Group
S. Zeinali; NPC-RT Process Group
Outline
• Natural Gas, Methanol and Propylene Chain
• Joint MTP® Technology
• Process
• Catalyst
• NPCRT’s new PVM® Technology
• Economy
• Methanol to Propylene
• Gas to Propylene
• Process Integrations
Natural Gas
• Huge resources of NG in Iran (world’s second resources)
• Constant developing markets in:
• Direct usage as less carbon-intensive fuel (distribution
networks)
• Power generation (power plants)
• Transport to international markets (pipelines, LNG
shipping)
• Added value chemicals production (petrochemical
complexes)
Methanol, domestic supply & demand
• Several domestic plants in operation
•
•
•
•
Shiraz Petrochemical Complex (200,000 T/A)
Khark Petrochemical Complex (660,000 T/A)
Fanavaran Petrochemical Complex (1,000,000 T/A)
Zagros Petrochemical Complex (2×1,650,000 T/A)
• Ongoing domestic plants
•
•
•
•
•
•
•
•
•
•
Khark Petrochemical Complex (1,300,000 T/A)
Kaveh Petrochemical Complex (2,100,000 T/A)
Marjan Petrochemical Complex (1,650,000 T/A)
Bushehr Petrochemical Complex (1,650,000 T/A)
Veniran Petrochemical Complex (1,650,000 T/A)
Petrochem Petrochemical Complex (1,650,000 T/A)
Kimia Pars Khavarmianeh Petrochemical Complex (1,650,000 T/A)
Farsa Shimi Petrochemical Complex (1,650,000 T/A)
Dipolymer Arian Petrochemical Complex (1,650,000 T/A
…
Supply is more than domestic demand, and major part of product are
being exported
Methanol, worldwide supply & demand
Thousands of metric tones
125000
115000
105000
Capacity
Production
95000
85000
75000
65000
55000
45000
35000
25000
2002
2004
2006
2008
2010
2012
2014
2016
2018
2020
Propylene, worldwide supply & demand
Thousands of metric tones
130000
120000
110000
100000
90000
80000
Capacity
Production
70000
60000
50000
2002
2004
2006
2008
2010
2012
2014
2016
2018
2020
Methanol to Olefin
methanol
Catalyst
olefins
paraffins
aromatics
What is Special about Zeolites?
• Pores with molecular dimensions leads to shape selectivity
• Narrow range of pores sizes in the solid because of
crystalline
materials
giving
better selectivity than
non-crystalline
Shapes Selectivity
Conversion of MeOH to Olefin
NG
(CH4)
MeOH
(CH3OH)
DME
(CH3OCH3)
Other C=
series
Water
(H2O)
C2=
(C2H4)
Acidic Behavior
ɣ-Alumina
Narrow pore Zeolites
C3=
(C3H6)
• SAPO- 34
• SAPO- 18
• Chabazite
Medium pore Zeolites
• ZSM -5
Paraffins
LPG,
Gasoline
• ZSM- 11
Wide pore Zeolites
Mordenite
ZSM-4
Faujasite (X and Y)
Water
(H2O)
Converting MeOH to Propylene
NG
(CH4)
Natural
Gas
CH4, Pure
SynGas
Processes
MeOH
(CH3OH)
DME
(CH3OCH3)
Other C=
series
No
Oxygenate
C3=
Methanol
Di-methyl Ether
Grade AA
CH3OCH3 (40% Mole)
CH3OH
Water
(100 Kg/Hr)
H2O (40% Mole)
Methanol
C2=
(C2H4)
* By default, recycles back to reaction
LPG
(4 Kg/Hr)
C3=
(C3H6)
Gasoline
(8 Kg/Hr)
Water
CH3OH (20% Mole)
CO, H2
(32 Kg/Hr)
Paraffins
LPG,
Gasoline
Water
(H2O)
(56 Kg/Hr)
C2=*
(~ 2 Kg/Hr)
Joint MTP® Project with Lurgi Oel.Gas.Chemie
• Started at 2003
• Joint development of a commercial scale of MTP® process
• Research studies on pilot plant scales
• Design, construction and startup of the first semi-commercial
MTP Demo Plant in the world
• Basic engineering of the first commercial MTP plant in the
world
MTP, Block Flow Diagram
HP Steam
DM Water
HP Condensate
Unit 1000
Steam System
Unit 1100
Cold Water System
Flare
Unit 1200
Refr. System
HC
C3=
MeOH, DME
MeOH
Unit 100
Reaction
Unit 300
Gas Separation
Unit 400
Compression
Unit 500
Purification
LPG
Gasoli
ne
Unit 200
Regeneration
Nitrogen, Plant Air, Instrument Air, Electrical Power, Fuel, LPG
for startup, etc.
MTP Key Features
• High propylene yield (more than 65% mole, on C basis)
• Simple process (low-cost propylene production)
• Simple fixed-bed adiabatic reactor system
• Simple well-known purification section
• Low pressure operation
• Added value by-products (LPG, Pyrolysis Gasoline)
NPC-RT Facilities
• Several microrecator setups with online analyzers
• Lab and pilot scale catalyst production setups
• 4×100 gr catatest setup (parallel beds)
• 1500 gr catalyst pilot plant with main separation units
• Semi-comercial catalyst production setup
• MTP demo plant with complete comercial features (worlds first
semi-comercial MTP plant)
• Complete analytical facilities
• Expert research and engineering team
NPCRT activities
• More than 8000 hours pilot plant run
• Development of a new catalyst with great performance, and
• Commercializing NPCRT‘s PVM® catalyst (patented)
• Process integration studies with focus on GTP, and
combinition to existing olefin plants
• New separation concepts
• New innovative reactor (patent preparation)
Scale-up History
Extruded NPC-RT catalyst
NPCRT proprietary catalyst
• Developed by NPC-RT (issued as patent)
• Zeolite type
• Promoted and improved formulation
• Confirmed in lab, bench and pilot scale performance tests
• Flexibility of catalyst for gasoline production (MTG)
• Low methane production
• Lower heavy hydrocarbon and higher light olefins production
versus commercial sample under MTP process conditions
• Increased selectivity to propylene by using some specific
promoters
Highlights of NPCRT catalyst
• Competitive performance (propylene selectivity, methanol
conversion & lifetime) versus commercial counterparts
• Mild processes conditions for catalyst manufacturing (100 ºC,
1 barg and non-corrosive starting materials)
• Economic manufacturing unit for mass catalyst production
• High mechanical strength (top & side)
Chemical composition of NPC-RT catalyst
Once-through pilot test results
Reaction: T= 480˚C, WHSV=0.9h-1, P=atm, MeOH/ H2O=1/1wt%,
MTP Combination with other Processes
• MTP as reaction section of a conventional naphtha based olefin
plant
• Better C3= to C2= ratio, better economies
• Moderate process condition (lower P and T) vs. olefin furnaces
• Not to much changes to existing plant
• Complete natural gas to propylene chain; GTP or GTPP
• Possibility for lower MeOH purification, better economies
• Possibility for using MTP process water for Syngas generation,
better economies
• MTP integrated with power plant
• Possibility for using MTP process water for power generation, better
economies
• DME with MTP
• Bigger DME section, more plant production flexibility
MTP Economies
250
300
350
400
450
500
70
FCI ($ Milion)
60
MeOH 280
MeOH 300
50
MeOH 320
MeOH 340
ROI %
40
Sensitivity to FCI
Base Case:
MeOH: 280 $/ton
Propylene: 1000 $/ton
FCI: $ 250 M
30
20
10
0
800
850
900
950
1000
1050
-10
Propylene Price $/ton
-20
1100
1150
1200
GTP Economies
Much better economy
Sensitiviuty Of IRR to NG Price
40
35
Propylene Price
1150 USD/ton
IRR (%)
30
1100 USD/ton
25
1000 USD/ton
20
900 USD/ton
15
800 USD/ton
10
700 USD/ton
5
600 USD/ton
500 USD/ton
0
0
5
10
NG Price (cent/m3)
15
20
Conclusions
• Methanol could have a key position in natural
gas value chain in natural-gas based
petrochemical industries
• Methanol can be effectively used as a
supplement or alternative to naphtha
• NPC-RT has developed effective catalysts
and technology to convert methanol to value
added higher hydrocarbons
• The technology has demonstrated in pilot
and demo scales
Conclusions (cont’d)
• The technology could be integrated with a
number of conventional petrochemical and
refining technologies
Thanks
M. Daftari