Unifying Concepts in Catalysis

Cluster of Excellence
Is oxidative coupling the royal road
for the valorization of methane to olefines?

R. Schomäcker, V. Fleischer, S. Parishan, J. Sauer, M. Baldowski,

K. Kwarpien, A. Thomas, S. Mavlyankariev, R. Horn, A. Trunschke,
P. Schwach, R. Schlögl, Y.Cui, N. Nilius, H.J. Freund, F. Rosowski
U. Simon, M. Yildiz, O. Görke, H. Godini, G. Wozny

Presentation at „Changing Landscape…“-Workshop,

Washington, DC, March 7-8, 2016
The Scenario
 Working hypothesis

Oxidative coupling of methane is economically viable, if:

- added value is high

- methane is not wasted
- energy demand is appropriate
- capital expenditure is reasonable
 Pioneering work

G.F. Keller, M.M. Bhasin, J. Catal. 1982, 73, 9 catalyst

M. Hinsen, M. Baerns, Chem. Z. 1983, 107, 223 catalyst
A.C. Jones, J.J. Leonardo et al., US patent 4 443644, 1984 periodic feed
strategy

160
140
120
100
papers

80 Reihe1
60
40
20
0
1985 1990 1995 2000 2005 2010

year
U. Zavyalova, M. Holen, R. Schlögl, M. Baerms, ChemCatChem, 2011, 3, 1935
 Milestone 1: The Lunsford Mechanism of OCM

methane activation
2CH 4

2[ Li  O  ] 2CH 3  2[ Li  O  ]H
catalyst
. Lunsford
regeneration mechanism product

[ Li  O 2 ] formation
1
O2 
2 C 2 H 6  H 2O

[ Li VO ]

• Optimal loading for initial activity: 0.5 wt% Li/MgO

• No stable Li/MgO-catalyst
• Still active after Li-Loss
• No selectivity
J. H. Lunsford, Angew. Chem. 1995, 107, 1059 – 1070;
Angew. Chem. Int. Ed. Engl. 1995, 34, 970 – 980
 Milestone 2: The first kinetic model

Z. Stansch, L. Mleczko, M.B. ,

Ind. Eng. Chem. Res. 1997, 36, 2568

LaO2O3 (27at%)/CaO
 Milestone 3: Mn-doped Na2WO4/SiO2

X.Fang et al, J. Mol. Catal. (China), 6 (1992) 427

X CH4 S C2 Y C2
Na2WO4/SIO2 0.11 0.75 0.08
MnOx/SiO2 0.16 0.34 0.07
Na2WO4/Mn/
SiO2 0.37 0.65 0.24

D.J. Wang, M.P. Rosynek, J.H. Lunsford, J. Catal. Z. Jiang, H. Gong, S. Li, Stud. Surf. Sci. Catal. 112 (1997)
155 (1995) 390 481

200 g batches with spray drying technology

H. Liu, X. Wang, D. Yang, R. Gao, Z. Wang, J. U. Simon, O. Görke, A. Bertold, S. Arndt, R. Schomäcker,
Yang, J. Nat. Gas. Chem. 17 (2008) 59 H. Schubert, Chem. Eng. J.168 (2011) 1352-1359
 Milestone 4: OCM at La2O3
EA = 39 kcal/mol 10 kcal/mol
CH4 COx CH4 CH3 CH4 CH3 CH4 CH3
[1] [4,7] [4,5]
[1]
O2 O2- O22- O- O2- [7]
650 °C EPR XPS EPR EPR XPS EPR XPS
[2,3] ?
La2O2CO3
CO2 IR

increase selectivity!
[6]
LaxFeyO3
[8]
LaxCeyOz
[1] C. Louis, T.L. Chang, M. Kermarec, T. Le Van, J.M. Tatibuët, M. Che, Colloids Surfaces A Physicochem. Eng. Asp. 72 (1993) 217
[2] T. Levan, M. Che, J.M. Tatibouet, M. Kermarec, J. Catal. 142 (1993) 18
[3] J.-L. Dubois, M. Bisiaux, H. Mimoun, C.J. Cameron, Chem. Soc. Japan Chemistry (1990) 967
[4] M.S. Palmer, M. Neurock, M.M. Olken, J. Am. Chem. Soc. 124 (2002) 8452
[5] C. Lin, K.D. Campbell, J. Wang, J.H. Lunsford, J. Phys. Chem. 90 (1986) 534
[6] Y. Sekine, K. Tanaka, M. Matsukata, E. Kikuchi, Energy and Fuels 23 (2009) 613
[7] C. Au, T. Zhou, W. Lai, C. Ng, Catal. Letters 49 (1997) 53
[8] V.J. Ferreira, P. Tavares, J.L. Figueiredo, J.L. Faria, Catal. Commun. 42 (2013) 50
[9] S. Gadewar, S.A. Sardar, P. Grosso, A. Zhang, V. Julka, P. Stolmanov, Continuous Process for Converting Natural Gas to Liquid
Hydrocarbons, U.S. Patent US8921625B2, 2014 (Siluria Technologies)
Milestone 5: unconventional approaches
 Who is who in OCM

Author Publications* Citations*

M. Baerns 47 1323
J.H. Lunsford 43 1696
V.R. Chaudhary 36 926
J.R.H. Ross 36 666
K. Fujimoto 33 728
J.B. Moffat 31 528
C. Mirodatos 29 334
A.G. Anshitz 25 261

* Web of Science, 25.7.2014

 The UNICAT concept

Multi scale approach for atomic to plant level

Model studies for understanding complexity
Feasibility studies in mini-plant

* table adopted from E. V. Kondratenko, M. Baerns

Handbook of Heterogeneous Catalysis, Vol. 6, Ch. 13.17, 2008
 Multi scale approach to OCM

G. Wozny
R. Schlögl M. Kraume
H.J. Freund
T. Risse H. Schubert

R. Horn A. Thomas

R. Schomäcker M. Driess

J. Sauer
M. Scheffler
 Mechanism of Oxidative Coupling of Methane

2 CH4 + O2 → C2H4 + 2 H2O (+ CO2)

COx
+ O2
+ O2 + O2
O2 CH4
C2H4
COx CH3 C2H6 C2H5
+ CH 3

O2ad O2ad + CH 3
* * O C2H6 O O

Origin of low selectivity

- OCM is initiated by oxygen activation (AFM, DFT, Model catalysts)
- Selective and inselective oxygen species at all catalysts (TAP, TPSR)
- Electron donors (dopants, defects) cause oxygen dissociation (AFM, Model catalyst)
- Formation of methyl radicals at selective oxygen species (Kinetics, KIE, Model cat.)
- Combustion of methane at inselective species (Kinetics, KIE)
- Parallel gas phase combustion at increased oxygen partial pressure (Profile R.)
K. Kwapien, J.Paier, J. Sauer, M. Geske, U. Zavyalowa, R. Horn, P. Schwach, A. Trunschke, R. Schlögl, Angew. Chem. Int, Ed. 2014, 53, 11-6
Y. Cui, X. Shao, M. Baldofski, J. Sauer, N. Nilius, H.J. Freund, Angew.Chem.Int.Ed. 2013, 52, 11385
B. Beck, V. Fleischer, S. Arndt, M. G. Hevia, A. Urakawa, P. Hugo, R. Schomäcker Catalysis Today 2014, 228, 212–218
The Puzzle of Information

How to get started?

Searching for more pieces?

Joining central pieces?

A simple example

2
A simple example

2
 Experiments in a TAP reactor

In collaboration with J. Perez-Ramires, ICIQ, Taragona, now ETH Zurich

Pump-probe experiments in a TAP reactor

- Increasing delay of CH4

leads to decrease of CO2
and C2H6 stays constant

- weakly adsorbed oxygen

leads to total oxidation
* + O2 *O2

- strongly adsorbed oxygen

is responsible for methyl
radical formation
*+O *O

- smaller ratio between

weakly and strongly
adsorbed oxygen at
Mn/Na2WO4/SiO2
Dynamic experiment

750 °C, 30 nml/min, 1g catalyst

S(C2) = 0.89

• C2 Selectivity unexpacted
high in dynamic experiments
at constant temperature

• less oxygen species on the

catalyst surface than in
steady state exp.

2
 Characteristics of MgO prior to reaction
S-MgO C-MgO SG-MgO

Mg oxidation Ultra pure commercial MgO Sol-gel synthesis

HT-MgO MW-MgO

Hydrothermal post treatment

Hydrothermal post treatment in microwave autoclave
Kwapien, Paier, Sauer, Geske, Zavyalova, Horn, 2
Schwach, Trunschke, Schlögl, Angew. Chem. Int. Ed., 2014, 53, 8774
 Deactivation of C-MgO
t=0h t = 230 h

t=6h t = 25 h t = 66 h

Rate of methane consumption decreases with decreasing number of

monoatomic steps observed with CO as probe molecule by IR

P. Schwach, M. G. Willinger, A. Trunschke, R. Schlögl ,

Angewandte Chemie International Edition 2013, 52, 11381–11384
 Structure sensitivity of MgO during reaction

Eley-Rideal mechanism

• CH4 adsorbes and is activated

• O2 leads to methyl radical formation
• Superoxide identified by EPR

Kwapien, Paier, Sauer, Geske, Zavyalova, Horn,

Schwach, Trunschke, Schlögl, Angew. Chem. Int. Ed., 2014, 53, 8774
 Mechanism of OCM at MgO

Kwapien, Paier, Sauer, Geske, Zavyalova, Horn,

Schwach, Trunschke, Schlögl, Angew. Chem. Int. Ed., 2014, 53, 8774
Baldowski, Sauer, unpublished
 Mechanism of OCM at MgO
Energy, Gibbs free energy (kJ/mol)
CH3−/H+ O2 TS Int-1a Int-1b Int-2
ads 28 O2 −
272 24
254 4
18 136
121 + O2 ~O2
10
217 ~O2 -5 − CH3
224

d(O-O)/d(Mg-O) 122/215 127/227 135/253

1013 K, 0.1 MPa
Kwapien, Paier, Sauer, Geske, Zavyalova, Horn,
Schwach, Trunschke, Schlögl, Angew. Chem. Int. Ed., 2014, 53, 8774
Baldowski, Sauer, unpublished
 Mo-doped CaO films on Mo(001)

Mechanism:
•Mo-donors in CaO transfer charges
into O2 molecules bound to surface
• Formation of pre-disscoiated O2-
species
• Final dissociation via electron
tunneling from STM tip

Experimental evidence:
• Work function increase after O2 dosage
only in the case of doped films

• no O2 adsorption at 300 K for pristine

CaO

Y. Cui, X. Shao, M. Baldofski, J. Sauer, N. Nilius, H.J. Freund,

Angew.Chem.Int.Ed. 2013, 52, 11385
 Mo-doped CaO films on Mo(001)

O-O
O2

8.0nm 8.0nm

As dosed O2: Molecular species After dissociation with STM tip

(scanning below 2.5 V sample bias) (electron injection with 3.0 eV energy)

Y. Cui, X. Shao, M. Baldofski, J. Sauer, N. Nilius, H.J. Freund,

Angew.Chem.Int.Ed. 2013, 52, 11385
 Doping of MgO with Fe

P. Schwach, M. Willinger, A. Trunschle, R. Schlögl

Angew.Chem.Int.Ed. 2013, 52, 11381
 OCM on MgO

CH3 CH4 CH3 COx

O2 O2- [Mg2+, HO-] HO2- [Mg2+, HO-]
133
CH4 58 241
180
Fe doping [2] or 114
[Mg2+, O2- ] N2O as oxidant [3] 119
increase selectivity
-7
114 103
CH3 226
O- [Mg2+, HO-] [Mg2+, O22- ] H2O
H2O
CH4 CH3 CH4
COx CH3
EA 0K [kJ/mol]
Gibbs Free Energy, 1013 K, 0.1 MPa
[1] K. Kwapien, J. Paier, J. Sauer, M. Geske, U. Zavyalova, R. Horn, P. Schwach, A. Trunschke, R. Schlögl, Angew. Chemie - Int. Ed. 53 (2014) 8774
[2] P. Schwach, M.G. Willinger, A. Trunschke, R. Schlögl, Angew. Chemie - Int. Ed. 52 (2013) 11381
[3] H. Yamamoto, H.Y. Chu, M.T. Xu, C.L. Shi, J.H. Lunsford, 142 (1993) 325
Bi-metallic Na2WO4 /Mn/SiO2 catalysts for OCM

• Provides/stores
lattice oxygen
• Works without gas
phase oxygen
• Deep oxidation
catalyst for methane

How does it OCM in transient

work? experiments

• Selective OCM
catalysts
• Needs oxygen
source to form
methyl radicals
 Support variation for MnxOy/Na2WO4/SiO2

silica support pre-catalyst catalyst

commercial
Impregnation Calcination
Na2WO4 · 2 H2O
Mn(ac)2 ·4 H2O
750°C

nanostructured
(SBA-15) Up-scaling of catalyst synthesis

M. Yildiz, Y. Aksu, U. Simon, K. Kailasam, O. Goerke, F. Rosowski,

R. Schomäcker, A. Thomas, S. Arndt Chem. Commun. 2014, 50, 14440
 Support variation for MnxOy/Na2WO4/SiO2

Distribution of
Mn-Na2WO4 on

commercial

Green - W
Red - Mn

nanostructured
(SBA-15)

silica supports

M. Yildiz, U. Simon, T. Otremba, K. Kailasam, Y. Aksu, A. Thomas, R. Schomäcker, S. Arndt Catalysis Today 2014, 228, 5-14
H.R. Godini, A. Gili, O. Görke, S. Arndt, U. Simon, A. Thomas, R. Schomäcker, G. Wozny, Catalysis Today, 2014, DOI
10.1016/j.cattod.2014.01,005
 Support variation for MnxOy/Na2WO4/SiO2

X Mn-Na2WO4/SBA-15
X X

Mn-Na2WO4/commercial silica

Testing in lab scale reactor at 750 °C (C2-Yield= 12 %)

In mini-plant membrane reactor at 810 °C (C2-Yield= 23 %)
M. Yildiz, Y. Aksu, U. Simon, K. Kailasam, O. Goerke, F. Rosowski,
R. Schomäcker, A. Thomas, S. Arndt Chem. Commun. 2014, 50, 14440
 Dynamic Experiments

• At reaction temperature the

catalyst is oxidized by air
pulse
• Reactor is purged with Helium
to remove oxygen in gas phase
and weakly adsorbed one

• Defined amount of methane is

dosed into the reactor

• Reaction mixture is analysed

by mass spectroscopy

 Catalyst activity can be

analyzed without gas phase
oxidation reactions
 Repetitive dynamic experiments

Molefraction (%)
• Repetitive methane pulses
allow to study the available
amount of oxygen

Na2WO4 (5%)/Mn(2%)@Quartz Na2WO4 (5%)/Mn(2%)@SBA15

O (µmol/gcat) 20.5 68.9
 OCM at Na2WO4/Mn/SiO2

• Infeasibility of various spectroscopic techniques

• mechanism proposed by analogy to other systems

CH4 COx CH4 CH3 COx

[1]
O2 O2,ads O2- HO2-

cus Mn doping [2]

increases activity
and selectivity
H2O
H2O CH3
O- O22-
CH4 COx CH3
[1] B. Beck, V. Fleischer, S. Arndt, M.G. Hevia, A. Urakawa, P. Hugo, R. Schomäcker, Catal. Today 228 (2014) 212
[2] S. Ji, T. Xiao, S. Li, C. Xu, R. Hou, K.S. Coleman, M.L.H. Green, Appl. Catal. 225 (2002) 271
Network of surface reactions at MnxOy/Na2WO4/SiO2
 OCM in a mini-plant reactor
Fluidized Bed Reactor Reactor performance

+ Isothermal reaction 2%Mn-2.2%Na2WO4/SiO2 catalyst, particle size 250-450 μm

Bed height: 10 cm, CH4:O2 = 1.7 to 10,
Feed Flow rate: 0.1 l/min – 40 l/min, 45 37
- Sensitive to free gas volume
g catalyst
OCM membrane reactor set-up

Alumina
 Performance indicators of the membrane reactor

2%Mn-5%Na2WO4/SiO2 catalyst (4 g), average particle size 250-450 μm

Contours were made by using 40 experimental data

 Reactor concept: Chemical looping

Operation steps:

1. O2 is dosed to oxidize
the catalyst

2. Reactor is purged with

inert gas to remove gas
phase oxygen

3. CH4 dosage to perform

OCM

4. Purge with He to remove

unconverted methane
 Continuous operation

Early pulses Late pulses Early pulses Late pulses Looping

XCH4 0.28
SC2 0.78
Y 0.22
STY 83
µmol(C2)
/g*h with diluent

Steady State
XCH4 0.29
SC2 0.63
Y 0.18
STY
µmol(C2) 529
/g*h

2 g catalyst, 1 ml CH4 pulse, 1 ml O2 pulse, 775 °C, 30 nml/min

 Continuous operation

800°C

2 g catalyst, 1 ml CH4 pulse, 1 ml O2 pulse, 30 nml/min

 Economic Analysis

Simulations with Aspen Plus & Aspen Process Economic Analyzer v8.8

Production capacity is one million tonnes per year

Ethylene price 947 Euro/tone

1. Case I (OCM Reaction Unit + CO2 separation Unit+Demethanizer

Unit+C2-Splitter Unit)
2. Case II (OCM Reaction Unit + CO2 separation Unit + Demethanizer
Unit + C2-Splitter Unit + Ethane Dehydrogenation Unit)
3. Case III (OCM Reaction Unit + C2H4 adsorption/Desorption Unit +
C2-Splitter Unit + Ethane Dehydrogenation Unit)
 OCM to Ethylene (Case I)

Amine scrubbing (30%wt MEA)

Energy needed: 8 GJ/t-CO2
Energy cost associated: 14.3 €/t-CO2

OCM reactor: Mn-Na2WO4/SiO2 catalyst

Membrane reactor (40% conv. & 62% sel.)
<5% N2 , dense membrane, air separation
Methane-cryogenic media cycle
Energy needed: 4.8 GJ/t-CO2
Energy cost associated: 104.4 €/t-C2H4
Propylene-cryogenic media cycle
Energy needed: 4.7 GJ/t-CO2
Cost associated: 8.8 €/t-C2H4
99.8 % Ethylen purity

44
 OCM to Ethylene (Case II)

Amine scrubbing (30%wt MEA)

Energy needed: 5.8 GJ/t-CO2
Energy cost associated: 12.8 €/t-CO2

OCM reactor:
Mn-Na2WO4/SiO2 cat.
40% conv. 62% sel.
air separation

EDH reactor (60% conv. & 65% sel.) Methane-cryogenic media cycle
Conventional performance Energy needed: 6.5 GJ/t-C2H4
Cost associated: 120.5 €/t-C2H4
Propylene-cryogenic media cycle
Compression
Energy needed: 0.4 GJ/t-C2H4 Energy needed: 3.8 GJ/t-C2H4
Electricity cost: 8.6 €/t-C2H4 Cost associated: 7.3 €/t-C2H4
99.9 % Ethylen purity
 OCM to Ethylene (Case III)

OCM reactor: Amine scrubbing (30%wt MEA)+Membrane (Hybrid)

Mn-Na2WO4/SiO2 cat. Energy needed: 10.93 GJ/t-CO2
40% conv. 62% sel. Energy cost associated: 22 €/t-CO2
air separation

EDH reactor (58% conv. & 63% sel.) Propylene-cryogenic media cycle
Conventional performance Energy needed: 3.38 GJ/t-C2H4
Cost associated: 10.42 €/t-C2H4
PSA/TSA activated carbon
99.9 % Ethylen purity
Energy needed: 1.10 GJ/t-C2H4
Energy cost associated: 11.11 €/t-C2H4
 Results of Economic Analysis

Case I Case II Case III

Economic Parameter
(Millions € per year)
Project Capital Cost 414 334 398
Operating Cost 962 907 820
Raw Material Cost 485 485 485
Utilities Cost 418 368 247
Product (C2H4) Sales 1020 1136 1208
Desired Rate of Return 15% 15% 15%

Pay Out Period (years) 7 5 4

 OCM integrated with dry reforming of methane

Further Modifications: Autothermal Reactor

H2,CO H2O
? Air separation
Reforming Rxn.

Air CH4, H2,

CO2 CO

Purification Unit
OCM Water CO2
C2H4
CH4 Reactor Separation Separation Demethanizer

C2H6
Reaction Unit Separation Unit

Further Options: OCM with methanol

OCM with styrene
OCM with Etylene oxide
OCM with oligomerization
 Conclusions

- The puzzling informations about OCM are essembled

in a complete picture

- Oxygen activation is the key step in OCM mechanism

- Selectivity is controlled by
different oxygen species

- Implications for new catalyst materials and their synthesis

- single phase, highly conductive, non-reducible, e-donor/acceptor

- New options with chemical looping technology

- Techno-economic analysis shows potential for further optimization

 Acknowledgments

Thank you for the attention!

The authors acknowledge the support from the Cluster of Excellence
„Unifying Concepts in Catalysis" coordinated by the Berlin Institute of
Technology - Technische Universität Berlin and funded by the German
research foundation - Deutsche Forschungsgesellschaft – DFG .

ThyssenKrupp Uhde

www.unicat.tu-berlin.de