Converting Methanol to Propylene

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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
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Outline

• Natural Gas, Methanol and Propylene Chain
• Joint MTP Technology
• Process
• Catalyst
• NPCRTs new PVM Technology
• Economy
• Methanol to Propylene
• Gas to Propylene
• Process Integrations

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Natural Gas

• Huge resources of NG in Iran (worlds 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)

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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 (21,650,000 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
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Methanol, worldwide supply demand
Thousands of metric tones
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Propylene, worldwide supply demand
Thousands of metric tones
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Methanol to Olefin
olefins paraffins aromatics
methanol
Catalyst
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What is Special about Zeolites?

• Pores with molecular dimensions leads to shape
  selectivity
• Narrow range of pores sizes in the solid because
  of crystalline giving better selectivity than
  non-crystalline materials

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Shapes Selectivity
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Conversion of MeOH to Olefin
DME (CH3OCH3)
Other C series
MeOH (CH3OH)
NG (CH4)
Water (H2O)
C2 (C2H4)
Acidic Behavior ?-Alumina
C3 (C3H6)

• Narrow pore Zeolites
• SAPO- 34
• SAPO- 18
• Chabazite
• Medium pore Zeolites
• ZSM -5
• ZSM- 11
• Wide pore Zeolites
• Mordenite
• ZSM-4
• Faujasite (X and Y)

Paraffins LPG, Gasoline
Water (H2O)
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Converting MeOH to Propylene
No Oxygenate C3 (32 Kg/Hr) LPG (4
Kg/Hr) Gasoline (8 Kg/Hr) Water (56
Kg/Hr) C2 ( 2 Kg/Hr)
Other C series
DME (CH3OCH3)
MeOH (CH3OH)
NG (CH4)
Natural Gas CH4, Pure
Methanol Grade AA CH3OH (100 Kg/Hr)
Di-methyl Ether CH3OCH3 (40 Mole) Water H2O (40
Mole) Methanol CH3OH (20 Mole)
C2 (C2H4)
C3 (C3H6)
SynGas Processes CO, H2
Paraffins LPG, Gasoline
Water (H2O)
By default, recycles back to reaction
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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

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MTP, Block Flow Diagram
Flare
DM Water
HP Steam
HP Condensate
Unit 1100 Cold Water System
Unit 1000 Steam System
Unit 1200 Refr. System
HC
C3
MeOH, DME
LPG
Unit 300 Gas Separation
Unit 100 Reaction
Unit 400 Compression
Unit 500 Purification
MeOH
Gasoline
Unit 200 Regeneration
Nitrogen, Plant Air, Instrument Air, Electrical
Power, Fuel, LPG for startup, etc.
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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)

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NPC-RT Facilities

• Several microrecator setups with online analyzers
• Lab and pilot scale catalyst production setups
• 4100 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

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NPCRT activities

• More than 8000 hours pilot plant run
• Development of a new catalyst with great
  performance, and
• Commercializing NPCRTs PVM catalyst (patented)
• Process integration studies with focus on GTP,
  and combinition to existing olefin plants
• New separation concepts
• New innovative reactor (patent preparation)

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Scale-up History
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Extruded NPC-RT catalyst
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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

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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)

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Chemical composition of NPC-RT catalyst
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Once-through pilot test results
Reaction T 480C, WHSV0.9h-1, Patm, MeOH/
H2O1/1wt,
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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

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MTP Economies
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GTP Economies
Much better economy
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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

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Conclusions (contd)

• The technology could be integrated with a number
  of conventional petrochemical and refining
  technologies

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Thanks
M. Daftari