Autothermic reforming of methane to produce syngas

- fluid mechanic mechanism of methane partition to partial oxidation

and to steam reforming (DEDEK)
- heat radiation mechanism
- reactions involved
- process conditions and considerations
- burner and reactor designs
- how mass balance and heat balance are determined

Definitions
DITA
Advantages and disadvantages
DITA
Process conditions and consideration
DEDEK
Reaction involved
DEDEK
Burner and reactor design
DEDEK
Fluid mechanic mechanism (POX and SRM)
DEDEK
Mass balance
DITA
Heat balance
DITA
Heat radiation
DEDEK

The autothermal reformer reactor and the secondary reformer are very similar. Both consist of a
compact refractory-lined pressure vessel with a burner, a combustion chamber and a catalyst bed.
The chemical reactions taking place are combinations of combustion and steam reforming
reactions dividing the reactor space into three reaction zones, as illustrated in Fig. 15 [30].
The burner is the key element of the autothermal and secondary reforming technology. The
burner provides the mixing of the feedstreams in a turbulent diffusion flame. The flame core has
a very high temperature, often above 2OOoC, and transfer of heat back to the burner from the
flame core by radiation and by recirculation of hot gas must be minimized. Hence, a burner
design based on the understanding of the fluid dynamic principles of the mixing and combustion
processes is necessary to obtain a safe operation and a satisfactory burner lifetime.
The combustion zone is the turbulent diffusion flame where the hydrocarbon and the oxygen are
gradually mixed and combusted. Normally, the principle of mixed-isburnt can be assumed,
because the exothermic combustion reactions consuming oxygen are very fast reactions. The
combustion proceeds as a substoichiometric process with an overall oxygen to hydrocarbon ratio
of 0.55-0.6. The combustion of methane takes place through numerous radial reactions, but in a
simplified model it can be considered as one molecular reaction, i.e. the highly exothermic
combustion of methane to carbon monoxide and water with an oxygen to methane ratio of 1.5.
Excess methane will be present at the combustion zone exit after all the oxygen has been
converted. Combustion of higher hydrocarbons can be simplified by similar reactions.

The so-called thermal zone is the part of the combustion chamber where further conversion of
the hydrocarbons proceeds by homogeneous gas phase reactions. The main reactions are thermal
methane reforming (1) and water-gas shift reaction (2), but various pyrolysis reactions involving
higher hydrocarbons also take place. The combustion chamber is followed by a fixed catalyst
bed, the catalytic zone, in which the final hydrocarbon conversion takes place through
heterogeneous catalytic reactions. At the exit of the catalytic zone the synthesis gas will be in
equilibrium with respect to the methane reforming (1) and shift reactions (2). The catalyst will
destroy any soot precursors formed in the combustion and thermal zones.

The top of the catalyst bed is exposed to the process gas leaving the combustion chamber at
temperatures of llOO-14OOC, and high thermal stability of the catalyst and the carrier system is
required. A nickel catalyst supported by a magnesia-alumina spine1 carrier has shown high
stability and activity for operation in autothermal and secondary reformers. The reactions are
mainly controlled by film diffusion at the outer catalyst pellet surface, meaning that the process
can be carried out at very high space velocities. In practice the catalyst volume is determined by
optimal flow distribution and pressure drop in the reactor.
The technologies have been known and applied in the industry for more than 50 years and must
today be considered quite mature.
from the principle of Le Chatelier, that at higher temperatures less methane and more carbon
monoxide are present in the equilibrium gas, and that methane content increases with pressure
and decreases with increasing ratio of steam to carbon. This is illustrated in Fig. 1 [l].
Methane autothermal reforming with CO2 and oxygen, a combination
of CO2 reforming and partial oxidation reactions (abbreviated
asMATR) has drawn significant interest in recent years in
alternative routes for conversion of natural gas (methane) to
syngas, a mixture of CO and H2, which can be used to produce
products with high added values, such as ammonia, hydrocarbons
and oxygenated compoundsThis process possesses
severaladvantages forsyngas productioninbotheconomicaland
technical aspects. First, it has low-energy requirements due to
the opposite contribution of the exothermic methane oxidation
and the endothermic CO2 reforming:

Second, MATR process allows the production of syngas with

a wider range of H2/CO ratio by manipulating the relative
concentrations of CO2 and O2 in feed. Oxygen in feed is alsohelpful for avoiding catalyst deactivation by carbon
deposition
In published articles, it was recommended that the
combining of endothermic reaction (Eq. (4)) and exothermic
reactions (Eqs. (1)(3)) proceeds more efficiently in a fluidized
bed reactor, thanks to the enhanced abilities in heat transfer
and fluidization of catalyst [610]. But the selected catalyst
must be well shaped and possess excellent attrition resistance
because the attrition of catalyst particles is a serious problem
in the fluidized bed reactor.
At the same time, it has been known for a long time that Nibased
catalysts possess high activity in the initial stage of the

reaction but suffer from rapid deactivation

Autothermal reforming (ATR), a combination of steam

reforming and partial oxidation reactions, is an advantageous
route for syngas production for both economical and
technical reasons. It has low-energy requirements due to the
opposite contribution of the exothermic methane oxidation
and endothermic steam reforming. The combination of these
reactions can improve the reactor temperature control and
reduce the formation of hot spots, avoiding catalyst
deactivation by sintering or carbon deposition. Moreover,
ATR allows the production of syngas with a wider range of
H2/CO ratio by manipulating the relative concentrations of
H2O and O2 in the feed
The increase in O2/CH4 feed ratio not only increases the
CH4 conversion but also improves the catalyst stability. The
excess of O2 avoids the deposition of carbonaceous residues
over the catalytic surface; however, the H2 and CO yields
also decrease due to the enhancing of total combustion.
The H2/CO product ratio can be manipulated by varying the
O2/CH4 feed ratio and it is possible to achieve the optimum
ratio for GTL processes (