1. References:
1. McCain, W.D., The Properties of Petroleum Fluids. 2 ed. 1990, Tulsa, OK: PennWell Books.
Olefin Production from Natural Gas 2.
3.
4.
5.
Weissermel, K. and H.-J. Arpe, Industrial Organic Chemistry. 2003, Weinheim: Wiley-VCH.
Weissermel, K., H.-J. Arpe, and A. Mullen, Industrial Organic Chemistry. 1978, Weinheim: VCH.
BASF advances novel syngas-to-olefins process, in Chemical Week. 2008.
Shenhua Baotou Coal-to-olefins project outputs qualified MTO grade methanol, in 21Tradenet. 2010.
6. Shale Gas - A Potential Boon for the US Olefins Industry. 2011, Marketresearch.com.
7. Williams to expand Geismar LA, olefins production facility, in IStockAnalyst.com. 2011.
8. China plant to use methanol to olefins technology, in Plastics News Report. 2011, Plastics News: Shanghai.
9. Chang J., R.J., Hariharan M., Total Petrochemicals Makes Big MTO Progress. ICIS.com.
MSc Graduate: J.J. Targett, MBA 10. Fallas, B., Dow picks Freeport, Texas, as site of new propylene plant, in Platts. 2011, McGraw Hill.
11. Hariharan, M., China's Latest Craze - methanol to olefins, in ICIS.com. 2010.
12. Hodges, P., TOTAL moves forward on methanol to olefins, in ICIS News. 2010, ICIS.
University of Aberdeen, Aberdeen, Scotland 13.
14.
Jagger, A., Total's MTO plant and projects in China could stimulate interest in MTO technologies, in ICIS.com. 2010.
Lemos, W., Shale gas revolution changes outlook for US ethylene industry, in ICIS News. 2011.
15. Leonard, K., Shell Oil may build plant in region, in Pittsburgh Tribune-Review. 2011: Pittsburgh.
16. Linde, VEBA OEL Cracker in Gelsenkirchen, NRW, Germany. 2011, Linde AG.
Production Routes to Olefins
Ethylene & Propylene: Feedstocks Refinery Gas
LPG
CH2 = CH2 & CH2 = CH – CH3 Methanol
Methane Ethane Propane Butane
Naphtha Higher Cuts
CH3OH
Building Blocks of Industrial Organic Chemistry C5+ C7/8+
Ethylene Feedstocks by Region, mid 1970s Thermal cracking furnesses for naphtha at VEBA OELGelsenkirchen, Germany
Methanol to Olefins
Region Western Europe USA World Thermal Cracking Thermal Cracking
Feedstock (% of Total) (% of Total) (% of Total)
“Refinery” Gases (C1-C4) 1 8 4 Catalytic
LPG (C3 & C4) 1 65 23 Dehydrogenation
Naphtha (C5-C9) 88 1 56
Other 10 26 17 FCC Catalytic Cracking
Ethylene
• Naphtha thermal “cracking” predominates worldwide Propylene
Butenes & Butadienes
• Naphtha cracking yields variable Propylene/Ethylene ratios depending mainly on feedstock composition
• LPG - a popular feedstock thanks to its relatively easy transportability; ~25% of LPG used for chemical synthesis Selected Recent Process Developments Natural Gas to Olefin Plant
• Lurgi launches MTO, Methanol to Olefins, process Announcements; 2010-11
• Direct production of olefins from the corresponding alkane is comparatively minor except in the USA
• Williams to expand ethylene & propylene
• UOP launches its own version of MTO production from shale gas in Geismar, LA
How hydrocarbons occur in nature – The 5 Reservoir Fluids • UOP offers catalyst for direct dehydrogenation of propylene • Shenhua Baotou commissions full scale
Fluid MTO unit using process developed by Dalian
Oils Volatile Oils Retrograde Wet Gases Dry Gases • Dalian Institute of Chemical Physics offers MTO process Institute of Chemical Physics with coal as
Gases feedstock for syngas methanol.
• BASF developing synthesis gas to olefins process
• Total successfully starts Methanol to Olefins
Stable liquid in Liquid in reservoir; gas Gas at initial reservoir Gas at reservoir Gas at reservoir
Physical Form reservoir & at STP emitted at STP conditions; at STP a liquid conditions; liquid phase conditions and at STP
pilot plant targeting propylene; Feluy, Belgium
(Standard Temp. & Pressure phase condenses condenses at STP
STP; 1atm & 298K) • Shell plans ethylene cracker in Appalachia –
likely feedstock is local, wet natural gas
API Density
(deg.) Max 45° Min 40° 40-60° n/a n/a
• Chevron to build new cracker in Texas with
shale gas as feedstock
Heptanes Plus
Content Above 20% 12.5-20.0% Below 12.5% ~0 0 •Wison (Nanjing) Clean Energy Co. Shanghai,
(mole %) will use UOP’s MTO technology to convert
methanol from natural gas or coal into olefins.
Producing Gas/Oil
Min. 3300 To Start up is planned for 2013.
Ratio Max. 2000 2000-3300
50,000+
Above 50,000 ∞
(SCF/STB)
• Dow to build propylene from propane unit in
Methanol to Olefins plant , Shenhua Baotou, China US by 2018