Converting Methanol to Propylene MTP M Daftari Gh

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 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) 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 2002 2004 2006 2008 2010 2012 2014 2016 2018 2020

Propylene, worldwide supply & demand Thousands of metric tones 130000 120000 1100000 90000 Capacity 80000 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 giving better selectivity than non-crystalline materials

Shapes Selectivity

Conversion of Me. OH to Olefin NG (CH 4) Me. OH (CH 3 OH) DME (CH 3 OCH 3) Other C= series Water (H 2 O) C 2= (C 2 H 4) Acidic Behavior ɣ-Alumina Narrow pore Zeolites C 3= (C 3 H 6) • 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 (H 2 O)

Converting Me. OH to Propylene NG (CH 4) Natural Gas CH 4, Pure Syn. Gas Processes Me. OH (CH 3 OH) DME (CH 3 OCH 3) Methanol Di-methyl Ether Grade AA CH 3 OCH 3 (40% Mole) CH 3 OH Water (100 Kg/Hr) H 2 O (40% Mole) Methanol Other C= series C 3= C 2= (C 2 H 4) * By default, recycles back to reaction (32 Kg/Hr) LPG (4 Kg/Hr) C 3= (C 3 H 6) Gasoline (8 Kg/Hr) Water CH 3 OH (20% Mole) CO, H 2 No Oxygenate Paraffins LPG, Gasoline Water (H 2 O) (56 Kg/Hr) C 2=* (~ 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 Unit 1200 Refr. System HC C 3= Me. OH, DME Me. OH Unit 100 Reaction Unit 300 Gas Separation Flare 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. 9 h-1, P=atm, Me. OH/ H 2 O=1/1 wt%,

MTP Combination with other Processes • MTP as reaction section of a conventional naphtha based olefin plant • Better C 3= to C 2= 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 Me. OH 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

GTP Economies Much better economy Propylene Price

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