The Shale Gas Revolution: A Methane-to-Organic Chemicals Renaissance? Or Methane: Fuel or Feedstock? Eric E. Stangland 2014 Frontiers of Engineering Irvine, California i Dow.com
Shale Gas for Chemical Production Typical Bakken Wellhead Gas Composition Ethane, 22% Propane, 13% C 4+, 7% Methane, 55% Inerts, 3% Source: Wocken et al, EERC presentation at 21st Williston Basin Petroleum Confernece, 2013 EES 2
Steam Cracking of Alkanes Natural Resources Feedstock Cracker Complex Products Olefins Separation EES 3
Light Hydrocarbon Cracker-8, TX Modern plant can make 1500 kta ethylene, or 171,000 kg/hr (376,000 lb/hr). EES 4
US Production of Light Hydrocarbons 250 2200 2000 Ethane, Propane Production (10 3 MMBtu) Production (10 9 MMBtu) 200 150 100 50 Methane Ethane Propane 1800 1600 Methane 1400 1200 EES 5 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 2014 Source: ICIS pricing, EIA Date
Chemical Investment Due to Shale Gas 2023 Projections US Gulf Cost Feedstock Pricing Fee edstock Value ($ $/MMBtu) 30 25 20 15 10 5 Methane (Henry Hub) Ethane (Mt. Belvieu) Propane (Mt. Belvieu) Naptha (Mt. Belvieu) 148 capital investment projects worth $100 B 637,000 direct/indirect new chemical jobs 0 /2001 /2003 /2005 /2007 /2009 /2011 /2013 1/1/ 1/1/ 1/1/ 1/1/ Date 1/1/ 1/1/ 1/1/ $244 B in new economic output Source: ICIS pricing, EIA Source: American Chemistry Council EES 6
2012 US Methane Utilization in kta CH 4 Fuel 516,782 (98.5%) NH 3 5,683 (74%) Methanol 667 (9%) Other 1,295 (17%) CO + H 2 H 2 O Chemicals 7,645 (1.5%) GTL fuels CO 2 CH 3 OH NH 3 By comparison, 2012 Ethylene Capacity = 24,000 kta Plenty of methane available for chemical use EES 7
Dilemma: Fuel or Feedstock? Current Future? Risk vs. Reward EES 8
Customer Valuation ) Consumer Va alue ($/MMBtu) 60 50 40 30 20 10 Methane (Henry Hub) US Retail Electricity US LPDE (Liner Grade) Contract Source: ICIS pricing, EIA 0 1/ 7/ 1/ 7/ 1/ 7/ /1/2011 /1/2011 /1/2012 /1/2012 /1/2013 /1/2013 US consumers are willing to pay more for plastic than electricity. Why not turn methane into plastic? EES 9
Known Methane-to Chemical-Routes (not-inclusive) Methanol-to-Olefins (MTO) Syngas Methanol Olefins Separation O 2 (ASU) Oxidative Methane e Coupling (OCM) Olefins Separation O 2 (ASU) Methane Pyrolysis Acetylene/ Syngas Hydrogenation Separation CO methanation O 2 (ASU) EES 10
Methane-to-Chemicals Efficiency vs. Cost Total Retained Carbon Efficien ncy (%) 80 70 OCM 20% 31% 49% MTO 60 SCE 42% 58% 44% 56% 50 MP Increasing 40 35% Sustainability? 30 65% 20 Total fixed capital by section Electricity POX 10 Generation C x H y reaction Reactant/product separation 0 0 10 20 30 40 50 Process Thermodynamic Efficiency (%) EES 11
Routes to Ethylene Methanol-to-Olefins (MTO) Syngas/ Methanol Olefins Separation Ethylene O 2 (ASU) Oxidative Methane e Coupling (OCM) Olefins Separation Ethylene O 2 (ASU) Olefins Separation Ethylene EES 12
Distillation Established technology Low energy efficiency i Easily scaled Low capital, low risk accounts for 90-95% of all separations in the petrochemical industry and up to 30% of overall industry energy usage. EES 13
Light Hydrocarbon Cracker-8, TX Cryogenic Distillation Train Cracking furnaces EES 14
Next Generation Chemical Plant What technology is needed to utilize all components of shale gas for organic chemical production? EES 15
New Chemistry Metal-loaded zeolite Butadiene Isoprene Isobutylene Cyclopentadiene New catalysts that utilize oxygen to convert methane (alkanes), exclusively to olefins New chemistries from lighter hydrocarbons to supplement C 4 and C 5 shortages EES 16
New Mass-transfer Agents Support Short-term: hybrid schemes Membrane Selective Layer Distillation Column High-temperature stable porous metals and ceramic membranes with high flux & selectivity Long-term: Distillation replacement MOFs Silver-salt Ionic Liquid BF 4 - H 3 C Ag + X - Carbons N N CH 2 H 2 C CH 2 CH 3 Membrane Cascade Absorption/Adsorption Sorbents with significantly ifi higher h selective capacity EES 17
Improved Computation and Logic 20 10 TS3 TS2 CH 2 O + SO 2 + H 0 CH 3 + SO 3 CH 3 SO 3 ( 2 E) y (H, kcal/mol) enthalpy -10-20 -30-40 -50 TS1: CH 3 SO 3 r(c-s)=2.06 Å TS2: CH 3 OSO 2 r(c-o)=2.30 Å CH 3 SO 3 ( 2 A 2 ) TS3: CH 3 OSO 2 r(c-o)=2.00 Å r(c-s)=2.26 Å CH 3 O + SO 2 CH 3 OSO 2 CH 2 O + HOSO 100 prediction profiler - desirability 50-60 CO 2 + H 2 O + SH -70 0 2 reaction 4 coordinate 6 8. 0-2 0 2-2 0 2-2 0 2-1.16 0.77 1.49 X1 X2 X3 Hybrid and advanced plants will Advanced ab initio modeling with require advanced process control complementary informatics and high- throughput experimentation EES 18
New US Chemical Industry is Dawning EES 19
Methane-to-Chemical Energy Usage 4 Re elative Exc cess Entha alpy Neede ed 3 2 1 0 Percentage of Enthalpy Utilization Separations and Heat Transfer Ideal Reaction 81% 71% 71% 92% 19% 8% 29% 29% -1 SCE MTO OCM MP EES 20