Methane to Syngas: Jan Lerou, Jan Lerou Consulting, LLC

The Changing Landscape of Hydrocarbon Feedstocks for Chemical Production
Implications for Catalysis: A Workshop

Methane to Syngas

Jan J Lerou
Jan Lerou Consulting, LLC
March 7, 2016

Methane to syngas process technologies
 Commercial technologies

 Steam reforming
 Partial oxidation
 Non-catalytic partial oxidation
 Auto-thermal reforming
 Catalytic partial oxidation

 Almost commercial technology

 Short Contact Time – Catalytic Partial Oxidation

 Oxygen Transfer Membranes – Praxair
 Dry Reforming

 Emerging Technologies
 Chemical Looping
 Tri-reforming

Commercial Process Technologies

SMR Technology

 Conventional
technology

 Capacity:

20 million standard cubic
feet/day

 Large Size:

~30m x ~30m x ~30 m

SMR Technology Today

Source: Basini, Eni

SMR Technology
 Limitations





Carbon formation at low steam/carbon
High conversion requires high temperatures
Excess steam production
Cooling in waste heat boiler to avoid Boudouard
carbon formation
 Low NOx levels required in stack

 Challenges





Lower the steam/carbon ratio
Low NOx burners
Material limitation in tube alloys
Reduce excess steam production by air preheat and
pre-reforming

SMR Catalyst Technology
Active metals:
Mostly Ni - Ru, Rh, Pd, Ir, Pt
Supports:
α - and -Al2O3, MgO, MgAl2O4, SiO2, ZrO2, CeO2, TiO2

Zoneflow Technologies LLC

Alantum

CATACEL - JM

Partial Oxidation Technology

Source: Basini, Eni

POX Technology
 Limitations

 Possibility of utilizing a “low value” feedstock.

 Reaction is exothermic (energy consumption is less)
 Environmentally friendly in terms of exhaust gases:
little NOx production

 Challenges

 Oxidation step is highly exothermic, reducing the
energy content of the fuel

 Cost of reaction materials are high

 Soot can easily emerge in the non-catalytic POX
process

Auto-thermal reforming technology

Source: Basini, Eni

ATR Technology
 Limitations

 Cost of oxygen

 Limitation in H2 pressure

 Limitation in exit temperature

 Requires waste heat boiler to avoid Boudouard carbon
formation

 Challenges

 Lower the steam/carbon ratio

 Increase CH4 conversion by increasing temperature

 Carbon free burner operation

 Increase throughput – vessel size

Comparison of the technologies

Operating conditions

CO2 emissions

Investment

Relative

Relative

H2/CO

Method
Temp (0C)

Press (bar)

SMR

750 - 900

15 - 40

3-5

100

100

ATR

850 - 1,000

20 - 40

1.6 - 2.65

74

60

POX

1,200 - 1,500

20 - 150

1.6 - 1.8

73

60

Pre-Commercial Process Technologies

Short Contact Time – Catalytic Partial Oxidation

Source: Basini, Eni

SCT-CPO vs SMR for a 55,000 m3/d unit
 Steam Reforming:

 Unit volume: approx. 11,000 m3

 Catalyst volume: 21 ton in 178 reactor tubes

 SCT-CPO:

 Unit volume: approx. 70 m3
 Catalyst volume: 0.8 ton

 Investment:

Source: Basini, Eni

OTM Autothermal Reformer

Source: Praxair

OTM Technology

Source: Praxair

Impact of OTM Technology

Source: Praxair

Dry Reforming
CH4 + CO2

2H2 + 2CO

 Last decades catalyst development focused
on screening a new catalyst to reach higher
activity, better stability toward sintering,
carbon deposition (coking), metal oxidation,
and forming of inactive chemical species

 Preferred catalytic metals:





Ni, Ru, Rh, Pd, Ir, and Pt
Ru & Rh have better activity and resistance to coking
Ni less expensive but high carbon formation
Co has shown potential although it is not as active

Dry Reforming

A. W. Budiman et al, Catal Surv Asia (2012) 16:183–197

Dry Reforming
 Few industrial applications

 One example: The JAPAN-GTL demo plant

Emerging Process Technologies

Chemical Looping Reforming

S. Luo, L. Zeng & L-S Fan, Annu. Rev. Chem. Biom. Engng, 2015, Vol. 6: 53-75
S. C. Bayham, A. Tong, M. Kathe & L-S Fan, WIREs Energy Environ 2016, 5:216–241

Chemical Looping Reforming
An alternative is to put a classical SMR reactor
inside the Chemical Looping Combustion loop

M. Ryden & A. Lyngfelt, International Journal of Hydrogen Energy 31 (2006) 1271 – 1283

Tri-reforming
Methane tri-reforming is a synergistic combination of the
three catalytic reforming processes

C. Song, Am. Chem. Soc. Div. Fuel Chem. Prep. (2000), 45 (4), 772-776

Tri-Reforming
Advantages

Disadvantages

• Direct use of flue gases

• Requires oxy plant

• High methane conversion

• Novel process

• No CO2 separation

• No commercial catalyst

• Desired H2/CO

• Requires high GHSV

• Minimal coke formation

• Heat & mass management

• Use of waste H2O/O2

• Inert gas handling

• Simplified process

Tri-reforming
Catalysts primarily Ni based with many
variations on promoters and supports
Ni/Ce-ZrO2 & Ni/ZrO2
Ni/MgO, Ni/MgO/CeZrO,
Ni/Al2O3
NiO-YSZ-CeO2
Ni/MgxTiyOz
Ni/SBA15
La-Ni/CeO2
Ni-CaO-ZrO2
Ni/ -SiC, Ni/CeO2

Ni/(CeO2,La2O3)/Al2O3
Rh-Ni/Ce-Al2O3
Ni/CeO2
Ce0.70La0.2Ni0.10O2-�
Ni-Mg/ -SiC
11%Ni@SiO2
Ni0Ce-Cr/Al2O3-ZrO2
Ni/MCM-41, Ni/SiC

M.H. Amin et al., APCChE 2015,. Melbourne (2015) 128-136