Journal of the American Chemical Society
Communication
(2) Gesser, H. D.; Hunter, N. R.; Prakash, C. B. Chem. Rev. 1985, 85,
235.
(3) Lunsford, J. H. Catal. Today 2000, 63, 165.
(4) Alvarez-Galvan, M. C.; Mota, N.; Ojeda, M.; Rojas, S.; Navarro,
R. M.; Fierro, J. L. G. Catal. Today 2011, 171, 15.
oxidation and reforming (autothermal reforming) also neces-
sitates costly separation steps and adjustments.17 In contrast,
the complete combustion of 1 equiv of methane with O2 from
the air gives the needed reaction and process heat for the
subsequent bi-reforming step. Furthermore, it also provides the
required CO2−2H2O mixture, which is mixed with 3 equiv of
methane (natural gas), giving the needed specific feed for bi-
reforming to produce exclusively metgas for the subsequent
methanol synthesis step (Scheme 3).20
(5) Tabata, K.; Teng, Y.; Takemoto, T.; Suzuki, E.; Banares, M. A.;
̃
Pena, M. A.; Fierro, J. L. G. Catal. Rev. 2002, 44, 1.
(6) Holmen, A. Catal. Today 2009, 142, 2.
̃
(7) Brown, M. J.; Parkyns, N. D. Catal. Today 1991, 8, 305.
(8) Zhang, Q.; He, D.; Zhu, Q. J. Nat. Gas Chem. 2003, 12, 81.
(9) Weissermel, K.; Arpe, H.-J. Industrial Organic Chemistry, 4th ed.;
Wiley-VCH: Weinheim, 2003.
(10) Olah, G. A.; Goeppert, A.; Prakash, G. K. S. Beyond Oil and Gas:
The Methanol Economy, 2nd ed.; Wiley-VCH: Weinheim, 2009, and
references therein.
Scheme 3. Oxidative Bi-reforming for Methanol Synthesis
(11) Roh, H.-S.; Koo, K. Y.; Jeong, J. H.; Seo, Y. T.; Seo, D. J.; Seo,
Y.-S.; Yoon, W. L.; Park, S. B. Catal. Lett. 2007, 117, 85.
(12) Roh, H.-S.; Koo, K. Y.; Joshi, U. D.; Yoon, W. L. Catal. Lett.
2008, 125, 283.
(13) Koo, K. Y.; Roh, H.-S.; Jung, U. H.; Yoon, W. L. Catal. Lett.
2009, 130, 217.
(14) Koo, K. Y.; Roh, H.-S.; Seo, Y. T.; Seo, D. J.; Yoon, W. L.; Park,
S. B. Int. J. Hydrogen Energy 2008, 33, 2036.
(15) Baek, S.-C.; Bae, J.-W.; Cheon, J. Y.; Jun, K.-W.; Lee, K.-Y. Catal.
Lett. 2011, 141, 224.
(16) Jun, H. J.; Park, M.-J.; Baek, S.-C.; Bae, J.-W.; Ha, K.-S.; Jun, K.-
W. J. Nat. Gas Chem. 2011, 20, 9.
(17) Rostrup-Nielsen, J.; Christiansen, L. J. Concepts in Syngas
Manufacture; Imperial College Press: London, 2011.
(18) Olah, G. A.; Goeppert, A.; Czaun, M.; Prakash, G. K. S. J. Am.
Chem. Soc. 2013, 135, 648.
(19) Olah, G. A.; Prakash, G. K. S. U.S. Patents 7,906,559, 2011;
8,133,926, 2012; 8,440,729, 2013.
(20) Using hydrogen-treated 15% NiO on MgO at 850 °C.
The self-sufficient oxidative bi-reforming of methane to
metgas can be carried out in a single bundled multi-tubular
reactor or in two separate reactors. It allows separate
combustion of 1 equiv of methane with the oxygen of the air
to give a CO2−2H2O flue gas mixture. After admixing of 3
equiv of fresh methane upstream of the flame followed by bi-
reforming,18−20 the formed metgas is then converted to
methanol in a well-known and industrially practiced synthesis
step using Cu/ZnO/Al2O3 or related catalysts. Furthermore,
the exothermic heat of reaction of methane combustion is more
than sufficient for the subsequent endothermic bi-reforming
process.18,19,21 Thus, methanol produced from the still-
abundant natural or shale gas resources that can last well into
the next century can be used as a replacement for petroleum oil
and its derived products while also decreasing their environ-
mental harm (global warming) via CO2 capture and recycling
(CCR) in a feasible, economic way for use in our previously
developed Methanol Economy.10
(21) Olah, G. A.; Prakash, G. K. S. U.S. Pat. Appl. 13791778, 2013.
The presently developed oxidative bi-reforming followed by
methanol synthesis thus achieves the long-sought-after goal of
transforming methane to methanol in high yield and selectivity
(eq 1) with no other oxidation products formed in this overall
economic and energetically efficient process, leaving very little,
if any, carbon footprint.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Support of our work by the Loker Hydrocarbon Research
Institute and the U.S. Department of Energy is gratefully
acknowledged.
REFERENCES
(1) Olah, G. A.; Molnar
Interscience: Hoboken, NJ, 2003.
■
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, A. Hydrocarbon Chemistry, 2nd ed.; Wiley-
10031
dx.doi.org/10.1021/ja405439c | J. Am. Chem. Soc. 2013, 135, 10030−10031