Converting Methanol to Propylene(MTP )

M. Daftari

Gh. Joukar; NPC-RT General ManagerS. Sahebdelfar; Head of NPC-RT Catalyst GroupA. Firouzi; Head of NPC-RT Process GroupM. Asadi; NPC-RT Catalyst GroupH. Alaiee; NPC-RT Engineering GroupS. 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

Propylene, worldwide supply & demand

Thousands of metric tones

olefinsparaffinsaromatics

methanol Catalyst

Methanol to Olefin

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 MeOH to Olefin

MeOH(CH3OH)

NG(CH4)

DME(CH3OCH3)

C3=(C3H6)

C2=(C2H4)

Other C=series

ParaffinsLPG,

Gasoline

Water(H2O)

Water(H2O)

Narrow pore Zeolites•SAPO- 34•SAPO- 18•Chabazite

Medium pore Zeolites•ZSM -5•ZSM- 11

Wide pore ZeolitesMordeniteZSM-4Faujasite )X and Y(

Acidic Behavior

ɣ-Alumina

Converting MeOH to Propylene

MeOH(CH3OH)

NG(CH4)

DME(CH3OCH3)

C3=(C3H6)

C2=(C2H4)

Other C=series

ParaffinsLPG,

Gasoline

Water(H2O)

SynGas Processes

CO, H2

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(

No Oxygenate

C3=

)32 Kg/Hr(

LPG

)4 Kg/Hr(

Gasoline

)8 Kg/Hr(

Water

)56 Kg/Hr(

C2=*

)~ 2 Kg/Hr(

* By default, recycles back to reaction

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

C3=

MeOH

Unit 300 Gas Separation

Unit 100 Reaction

Unit 400 Compression

Unit 500 Purification

LPG

Gasoline

MeOH, DMEHC

Unit 1100 Cold Water System

Unit 1000 Steam System

Unit 1200 Refr. System

Unit 200 Regeneration

Nitrogen, Plant Air, Instrument Air, Electrical Power, Fuel, LPG for startup, etc.

FlareDM WaterHP Steam HP Condensate

MTP, Block Flow Diagram

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

Reaction: T= 480˚C, WHSV=0.9h-1, P=atm, MeOH/ H2O=1/1wt%,

Once-through pilot test results

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

GTP Economies

Sensitiviuty Of IRR to NG Price

0

5

10

15

20

25

30

35

40

0 5 10 15 20

NG Price )cent/m3(

IRR

)%

(

1150 USD/ton

1100 USD/ton

1000 USD/ton

900 USD/ton

800 USD/ton

700 USD/ton

600 USD/ton

500 USD/ton

Propylene Price

Much better economy

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