Heterogeneous Catalysts for the Thermal Conversion of Methane to Products

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1 Heterogeneous Catalysts for the Thermal Conversion of Methane to Products Workshop on Advances in Conversion of Methane to Fuels and Chemical Stanford University Stanford, CA November 7, 2017 Alexis T. Bell Department of Chemical and Biomolecular Engineering University of California Berkeley, CA 94720

Brent Gunnoe University of Virginia Johannes Lercher

2 Source Materials Alexis T. Bell, (Chair) University of California, Berkeley Montgomery Alger Pennsylvania State University Maria Flytzani-Stephanopoulos, Tufts University T. Brent Gunnoe University of Virginia Johannes Lercher Pacific Northwest National Laboratory James Stevens The Dow Chemical Company (retired) Published by the National Academies in 2016

3 Source Materials

4 Outline Background and motivation Oxidative coupling of methane catalysts and processes Methane pyrolysis Direct oxidation of methane to methanol Direct oxidation of methane to formaldehyde Outlook and Perspective for future research

5 Shale Gas Boom: Impact on American Chemical Industry The rapid growth in shale gas production in the US has made methane and attractive and relatively inexpensive source of carbon for fuels and chemicals

6 Shale Gas Boom: Impact on American Chemical Industry The price of NG in the US has fallen since 2005 from ~ $9/MM BTU to ~ $2.5 MM BTU in 2015 Over the same period the price of NG in Europe and Asia has risen significantly relative to the US Likewise the cost oil on a BTU basis has risen

Shale Gas Boom: Impact on American Chemical Industry FIGURE 1-1 Relative position of the U.S. petrochemical production costs SOURCE American Chemistry Council

7 Shale Gas Boom: Impact on American Chemical Industry FIGURE 1-1 Relative position of the U.S. petrochemical production costs SOURCE American Chemistry Council (American Chemistry Council, 2015b) During the past 12 years, the US has moved from having the highest production costs for chemicals to being one of the lowest

8 Shale Gas Boom: Impact on American Chemical Industry The shale gas boom has led to rapid increases in capital investments, number of jobs, economic output, and new tax revenue

9 Components of Natural Gas Natural Gas: CH 4, C 2 H 6, C 3 H 8 Chemical Feedstocks: CO/H 2, CH 2 =CH 2, CH 3 CH=CH 2, CH 2 =CH- CH=CH 2, C 6 H 6 All of the components of natural gas can be converted to fuels and chemicals

10 Options for Using Shale Gas What else can be made from CH 4 in addition to CO/H 2? In principle, shale gas can be used to produce all chemical intermediates needed for the chemical industry

11 Options for Converting Methane to Chemicals Conversion of Methane Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Steam Reforming: Dry Reforming: Oxidative Coupling: Partial Oxidation: CH 4(g) + H 2 O (g) CO (g) + 3 H 2(g) CH 4(g) + CO 2(g) 2 CO (g) + 2 H 2(g) CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4(g) + O 2(g) H 2 C=O (g) + H 2 O (g) We will look at each of the options with an eye towards determining what is new and perspective

12 Options for Converting Methane to Chemicals Conversion of Methane Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Steam Reforming: Dry Reforming: Oxidative Coupling: Partial Oxidation: CH 4(g) + H 2 O (g) CO (g) + 3 H 2(g) CH 4(g) + CO 2(g) 2 CO (g) + 2 H 2(g) CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4(g) + O 2(g) H 2 C=O (g) + H 2 O (g) We will look at each of the options with an eye towards determining what is new and perspective

13 Schematic of a Fischer-Tropsch Plant Biomass Natural Gas CO +H 2 Syngas generation 45% of CAPEX Fischer-Tropsch synthesis 15% of CAPEX Product separation and upgrading 20% of CAPEX $83,000/bbl oil equivalent

14 Economic of NG Conversion to Liquid Fuels 2016 DOE/NETL-2013/1597 Today s NG costs ~ $2.50/MMBTU and crude oil costs ~ $50/bbl, which make the economics for GTL prohibitive

15 Options for Converting Methane to Chemicals Conversion of Methane Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Steam Reforming: Dry Reforming: Oxidative Coupling: Partial Oxidation: CH 4(g) + H 2 O (g) CO (g) + 3 H 2(g) CH 4(g) + CO 2(g) 2 CO (g) + 2 H 2(g) CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4(g) + O 2(g) H 2 C=O (g) + H 2 O (g) We will look at each of the options with an eye towards determining what is new and perspective

16 Oxidative Coupling of Methane (OCM) Methane pyrolysis > 2010 Membrane reactor Most of the publication on OCM catalysts were reported between 1985 and 2005 Since 2005 there has been a renewed level of interest in OCM E. V. Kondratenko et al., Catal. Sci. Technol. 2017, 7,

17 Oxidative Coupling of Methane (OCM) Methane pyrolysis > 2010 Membrane reactor Catalysts tested since 2010 do not differ significantly from those tested earlier Only four catalysts lie above the 30% yield line No significant breakthroughs in OCM catalyst performance have been achieved by using single-pass reactors with O 2 since 2010 E. V. Kondratenko et al., Catal. Sci. Technol. 2017, 7,

18 Catalyst Engineering Mn x O y -Na 2 WO 4 /SiO 2 Use of SBA-15 as a support results in a highly active catalyst Cat-1 provides Y C2 = 8.5% at X CH4 = 13% M. Yilidz et al., Chem. Commun., 2014, 50,

Oxidative Coupling of Methane (OCM) - 1985-2016 Methane pyrolysis Membrane reactor H.R. Godini et al., Fuel Proc. Technol., 2013, 106, 684-694. E. V. Kondratenko et al., Catal.

19 Oxidative Coupling of Methane (OCM) Methane pyrolysis Membrane reactor H.R. Godini et al., Fuel Proc. Technol., 2013, 106, E. V. Kondratenko et al., Catal. Sci. Technol. 2017, 7, Y C2 and X CH4 depend on reactor choice Highest Y C2 is obtained with a membrane reactor A significant fraction of the byproducts are CO and CO 2

20 Catalyst Engineering Membrane Reactor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Bi 1.5 Y 0.3 Sm 0.2 O 3-δ Using a membrane reactor it is possible to achieve Y C2 = 40% at X CH4 = 80% N. H. Othman et al., J. Membr. Sci., 2015, 488, 182

and FTS it is possible to achieve Y C2 = 38% at X CH4 =

21 Combined OCM and Fischer-Tropsch Synthesis Mn x O y -Na 2 WO 4 /SiO 2 Mn-Ru/TiO 2 OCM only OCM +FTS By combining OCM and FTS it is possible to achieve Y C2 = 38% at X CH4 = 64% E. V. Kondratenko, U. Rodemerck, ChemCatChem, 2014, 5, 697

22 Combined OCM and Dry Reforming of Methane (DRM) Ni/Al 2 O 3 Mn x O y -Na 2 WO 4 /SiO 2 Coupling of OCM and DRM enables good heat integration C 2 yields of 36% at X CH4 = 60% can be achieved H. R. Godini et al., Fuel Process technol., 2013, 106,

23 Proposed Dual Membrane for OCM/DMR H. R. Godini et al., Chem. Eng. Process, 2013, 74, The double membrane OCM/DRM is projected to produce a C2 yield of 20% for X CH4 = 63% 90% of the CO 2 produced by OCM is converted to a H 2 /CO = 1.0 mixture

24 Siluria Pilot Plant for Converting Methane to Ethene Siluria demonstration plant in La Porte, TX May be an option for conversion of stranded gas to marketable products

Conversion of Methane Oxidative Coupling: Overall Conclusions for OCM CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) Findings - Limited catalysts with single-pass ethene yields above 30% - Higher C2

25 Conversion of Methane Oxidative Coupling: Overall Conclusions for OCM CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) Findings - Limited catalysts with single-pass ethene yields above 30% - Higher C2 yields can be obtained using a membrane reactor - Coupling OCM with FTS, DRM, or ETL is an economically attractive option - Capital and operating costs are high relative to ethane steam cracking Conclusions Cost of ethene produced by OCM is 2-3x higher than by steam cracking OCM might be useful for converting stranded gas

26 Options for Converting Methane to Chemicals Conversion of Methane Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Steam Reforming: Dry Reforming: Oxidative Coupling: Partial Oxidation: CH 4(g) + H 2 O (g) CO (g) + 3 H 2(g) CH 4(g) + CO 2(g) 2 CO (g) + 2 H 2(g) CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4(g) + O 2(g) H 2 C=O (g) + H 2 O (g) We will look at each of the options with an eye towards determining what is new and perspective

Pyrolysis of Methane to Chemicals Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) + 1.

Principle products are ethene, benzene and naphthalene Process requires > 1300 K,

27 Pyrolysis of Methane to Chemicals Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Catalyst is stable and does not form coke Principle products are ethene, benzene and naphthalene Process requires > 1300 K, resulting in high energy demand and CO 2 emissions X. Bao and coworkers, Sci., 344, 616, 2014

28 Options for Converting Methane to Chemicals Conversion of Methane Pyrolysis: CH 4(g) 1/6 C 6 H 6(g) H 2(g) CH 4(g) 1/2 C 2 H 4(g) + H 2(g) Steam Reforming: Dry Reforming: Oxidative Coupling: Partial Oxidation: CH 4(g) + H 2 O (g) CO (g) + 3 H 2(g) CH 4(g) + CO 2(g) 2 CO (g) + 2 H 2(g) CH 4(g) + ½ O 2(g) ½ C 2 H 4(g) + 2 H 2 O (g) CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4(g) + O 2(g) H 2 C=O (g) + H 2 O (g) We will look at each of the options with an eye towards determining what is new and perspective

29 Oxidation of Methane to Methanol kg CH3OH kg cat -1 h -1 Solid black dots heterogeneous catalysts reported between Solid red dots heterogeneous catalysts reported since 2010 Open black and red circles homogeneous catalysts E. V. Kondratenko et al., Catal. Sci. Technol. 2017, 7, With one exception, none of the heterogeneous catalysts listed can achieve selectivities or productivities that are of industrial interest

30 Protocol for Preparing Precipitated Fe on SiO 2 C. A. G. Fajardo et al., Catal. Commun. 2008, 9,

31 Activity and Selectivity of Precipitated Fe on SiO 2 At 750 o C, a methanol yield of 10 % can be achieved for X CH4 = 14% C. A. G. Fajardo et al., Catal. Commun. 2008, 9,

32 Sequential Oxidation of Methane to Methanol A variety of Cu cations clusters exchanged into zeolites have been shown to be competent for carrying out the sequential oxidation of methane to methanol

CH 3 OH [Cu 2 (µ-oh) 2 ] 2+ [Cu 2 (µ-o) 2 ] 2+ + H 2 O S. Grunder et al., Nature Comm. DOI: 10.

33 Sequential Oxidation of Methane to Methanol Partial Oxidation: CH 4(g) + ½ O 2(g) CH 3 OH (g) CH 4 + [Cu 2 (µ-o) 2 ] 2+ [Cu 2 (CH 3 O)(OH)] 2+ [Cu 2 (CH 3 O)(OH)] 2+ + H 2 O [Cu 2 (µ-oh) 2 ] 2+ + CH 3 OH [Cu 2 (µ-oh) 2 ] 2+ [Cu 2 (µ-o) 2 ] 2+ + H 2 O S. Grunder et al., Nature Comm. DOI: /ncomms8546 Low yields Cyclical operation M. H. Groothaert et al., J. Am. Chem. Soc., , 1394

34 Sequential Oxidation of Methane to Methanol Particularly high yields of CH 3 OH can be achieved by O 2 pretreatment at 200 o C followed CH 4 exposure at this temperature P. Tomkins et al., Acct. Chem. Res., 2017, 50,

Sequential Oxidation of Methane to Formaldehyde Solid black dots heterogeneous catalysts reported between 1985-2010 Solid red dots heterogeneous catalysts reported since

35 Sequential Oxidation of Methane to Formaldehyde Solid black dots heterogeneous catalysts reported between Solid red dots heterogeneous catalysts reported since 2010 No studies published since 2010 have reported H 2 C=O selectivity > 50% for X CH4 > 3% One of the issues is that H 2 C=O decomposes to CO and H 2 at elevated temperatures

36 Summary and Outlook E. V. Kondratenko et al., Catal. Sci. Technol. 2017, 7,

37 Summary and Outlook OCM coupled with DRM, FTS, or ETL may offer potential for the utilization of stranded NG to produce ethene Partial oxidation of methane to methanol or formaldehyde appears to be far from achieving productivity levels required to become commercial

38 Environmental Impact of Different Technologies The CO 2 footprint for producing ethene via OCM is comparable to that for producing it via SC of ethane Production of ethene via MTO has a higher CO 2 footprint than ethane SC

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