Methane to Syngas

Jan J Lerou

Jan Lerou Consulting, LLC

March 7, 2016

The Changing Landscape of Hydrocarbon Feedstocks for Chemical Production

Implications for Catalysis: A Workshop

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 Boudouardcarbon 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

Supports:

α - and γ-Al2O3, MgO, MgAl2O4, SiO2, ZrO2, CeO2, TiO2

Active metals:

Mostly Ni - Ru, Rh, Pd, Ir, Pt

Zoneflow Technologies LLC CATACEL - JMAlantum

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

Method

Operating conditions

H2/CO

CO2 emissions Investment

Temp (0C) Press (bar) Relative Relative

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

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

CH4 + CO2 2H2 + 2CO

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

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

Methane tri-reforming is a synergistic combination of the

three catalytic reforming processes

Tri-Reforming

Advantages

• Direct use of flue gases

• High methane conversion

• No CO2 separation

• Desired H2/CO

• Minimal coke formation

• Use of waste H2O/O2

• Simplified process

Disadvantages

• Requires oxy plant

• Novel process

• No commercial catalyst

• Requires high GHSV

• Heat & mass management

• Inert gas handling

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/β-SiC, Ni/CeO2

Ni/(CeO2,La2O3)/Al2O3

Rh-Ni/Ce-Al2O3

Ni/CeO2

Ce0.70La0.2Ni0.10O2-𝛿Ni-Mg/β-SiC

11%Ni@SiO2

Ni0Ce-Cr/Al2O3-ZrO2

Ni/MCM-41, Ni/SiC

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