Conversion C i of f Sh Shale l Gas G (both (b th CH4 and d C2H6) to Chemicals: Relocating the USGC to t PA

Robert M Rioux Department of Chemical Engineering The Pennsylvania State University Pennsylvania Institutes for Energy and Environment 165 Fenske Laboratory University Park, PA 16801

In general, we are not good at converting C1/C2 to higher Cn or oxygenated compounds

The predominant reason is because chemical bonds in these molecules are some of the strongest known. Natural Gas Wet Gas

439 kJ/mol

350 kJ/mol

423 kJ/mol

Most reactions involving these reactions are endergonic (not p ), so heat must be added spontaneous), This is the primary reason why we burn methane, lots of energy harnessed in one little molecule

However, methane is the primary source of H2 and versatile syn-gas (CO/H2)

Methane steam reforming is well-established large scale method for production of H2 CH4 + H2O CO + 3H2
(Hrxn = 200 kJ/mol)

Dry reforming allows access to different CO:H2 ratio but process is not established on an industrial scale CH4 + CO2 2CO + 2H2
(Hrxn = 220 kJ/mol)

Deconstruct CH4 to oxidized carbon intermediate which is subsequently re-reduced CO + 2H2 CH3OH (methanol synthesis) nCO + (2n+1) H2 CnH(2n+2) + nH2O (Fischer-Tropsch synthesis) Methanol formaldehyde; Methanol gasoline (MTG)
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Direct conversion of methane to chemicals

Oxidative-coupling of methane (OCM) 2CH4 + O2 = C2H4 + 2H2O (Hrxn = -240 240 kJ/mol)
Reaction is exothermic, still conducted at high temperatures (750-950C) Equilibrium-limited Catalyst is very complex, complex multiple functionality don dont t know how it works Catalyst design/development needed Real incentive though to seek out catalyst that operates at lower temperatures (increased equilibrium conversion)

Methane dehydroaromatization 6CH4 C6H6 + 9H2

Reaction is highly endothermic Reaction is equilibrium-limited use catalytic membrane reactors to remove hydrogen y demonstrate g good selectivity y to benzene ( (~60%) ) but low y yield Catalyst Catalyst is bifunctional Mo/H-ZSM-5 (relative simple, cheap to manufacture) BTX chemicals is a billion dollar chemical industry
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Wet Gas from Marcellus is predominantly ethane

Well-established routes for converting ethane to ethylene naptha cracking and steam cracking Marcellus-derived ethane would be steam-cracked to ethylene
Steam cracking of ethane dates back to 1891 (Shukhov cracking process) US patent (1,049,667) on June 8, 1908 modification of Shukov cracking process Initiation reactions Hydrogen abstraction occurs where a free radical removes a hydrogen atom from another molecule, turning the second molecule into a free radical. Radical decomposition occurs where a free radical breaks apart into two molecules, one an alkene, , the other a free radical. This is the process p that results in the alkene products of steam cracking. Radical addition occurs when radical reacts with an alkene to form a single, larger free radical radical.

CH3CH3 2 CH3

CH3 + CH3CH3 CH4 + CH3CH2

CH3CH2 CH2=CH2 + H

CH3CH2 + CH2=CH2 CH3CH2CH2CH2

These processes are involved in forming the aromatic products that result when heavier feedstocks are used.
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World-scale ethylene cracker processes 1 MMT of ethane /yr

Ruwais EU2 (ethane cracker)

T t l Developmental Total D l t l cost t is i $1.5 $1 5 billion billi 1 Estimated Marcellus ethane output is 12 billion lbs/yr amounts to 4 world-scale crackers2
1http://www.glgroup.com/News/Shell-First-to-Announce-Large-Ethylene-Unit-in-Marcellus-Region-%28Part-1-of-2%29-54290.html 2http://www.glgroup.com/News/Is-Ethylene-Production-in-the-Cards-for-the-Marcellus-Shale-Region--52340.html

Ethylene in Northeast builds a PE and epoxide business

Ethylene investments generally bring in investments in derivatives, mainly Polyethylene and Ethylene Oxide derivatives1

7 Image taken from http://en.wikipedia.org/wiki/Ethylene#Alkylation