Feedstocks Methanol Refinery Gas LPG Naphtha Higher Cuts CH 3 OH Methane Ethane Propane Butane C5+ C7/8+ Methanol to Olefins Thermal Cracking Thermal Cracking Catalytic Dehydrogenation FCC Catalytic Cracking Ethylene Propylene Butenes & Butadienes MSc Graduate: J.J. Targett, MBA University of Aberdeen, Aberdeen, Scotland References: 1. McCain, W.D., The Properties of Petroleum Fluids. 2 ed. 1990, Tulsa, OK: PennWell Books. 2. Weissermel, K. and H.-J. Arpe, Industrial Organic Chemistry. 2003, Weinheim: Wiley-VCH. 3. Weissermel, K., H.-J. Arpe, and A. Mullen, Industrial Organic Chemistry. 1978, Weinheim: VCH. 4. BASF advances novel syngas-to-olefins process, in Chemical Week. 2008. 5. 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. 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. 13. Jagger, A., Total's MTO plant and projects in China could stimulate interest in MTO technologies, in ICIS.com. 2010. 14. 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. Olefin Production from Natural Gas Region Feedstock Western Europe (% of Total) USA (% of Total) World (% of Total) “Refinery” Gases (C1-C4) 1 8 4 LPG (C3 & C4) 1 65 23 Naphtha (C5-C9) 88 1 56 Other 10 26 17 Ethylene Feedstocks by Region, mid 1970s • Naphtha thermal “cracking” predominates worldwide • 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 • Direct production of olefins from the corresponding alkane is comparatively minor except in the USA How hydrocarbons occur in nature – The 5 Reservoir Fluids Natural Gas to Olefin Plant Announcements; 2010-11 • Williams to expand ethylene & propylene production from shale gas in Geismar, LA • Shenhua Baotou commissions full scale MTO unit using process developed by Dalian Institute of Chemical Physics with coal as feedstock for syngas methanol. • Total successfully starts Methanol to Olefins pilot plant targeting propylene; Feluy, Belgium • Shell plans ethylene cracker in Appalachia – likely feedstock is local, wet natural gas • Chevron to build new cracker in Texas with shale gas as feedstock •Wison (Nanjing) Clean Energy Co. Shanghai, will use UOP’s MTO technology to convert methanol from natural gas or coal into olefins. Start up is planned for 2013. • Dow to build propylene from propane unit in US by 2018 Production Routes to Olefins Ethylene & Propylene: CH 2 = CH 2 & CH 2 = CH – CH 3 Building Blocks of Industrial Organic Chemistry Fluid Oils Volatile Oils Retrograde Gases Wet Gases Dry Gases Physical Form (Standard Temp. & Pressure STP; 1atm & 298K) Stable liquid in reservoir & at STP Liquid in reservoir; gas emitted at STP Gas at initial reservoir conditions; at STP a liquid phase condenses Gas at reservoir conditions; liquid phase condenses at STP Gas at reservoir conditions and at STP API Density (deg.) Max 45° Min 40° 40-60° n/a n/a Heptanes Plus Content (mole %) Above 20% 12.5-20.0% Below 12.5% ~0 0 Producing Gas/Oil Ratio (SCF/STB) Max. 2000 2000-3300 Min. 3300 To 50,000+ Above 50,000 ∞ Thermal cracking furnesses for naphtha at VEBA OELGelsenkirchen, Germany Selected Recent Process Developments • Lurgi launches MTO, Methanol to Olefins, process • UOP launches its own version of MTO • UOP offers catalyst for direct dehydrogenation of propylene • Dalian Institute of Chemical Physics offers MTO process • BASF developing synthesis gas to olefins process Methanol to Olefins plant , Shenhua Baotou, China