History of Steam Methane Reforming (SMR)

The first patents on steam methane reforming of natural gas were awarded to BASF in
1926 and the first reforming plants were built in the 1930s. As Germany had no
natural gas available, the methane needed for experiments was synthesized from
carbon monoxide and hydrogen; Schiller is succeeded in reforming methane using a
nickel catalyst. Then, a licensing agreement transferred the BASF technology to
Standard Oil of New Jersey who began to produce hydrogen for use in its Baton
Rouge refinery in 1931. After that, a steam reformer was commissioned by ICI in
Billingham in 1936 and two tubular reformers capable of operating at around 15
atmospheric pressure were commissioned in 1962 while one operating at 40atm
pressure commissioned by Topsoe less than 5 years later.

Significance of Steam Methane Reforming (SMR)
In a steam methane reforming (SMR) process two main reactions are involved:
CH
4
+ H
2
O CO + 3H
2
, H = 206 kJ/mol
CO + H
2
O CO
2
+ H
2
, H = -41 kJ/mol
The first reaction is reforming itself, while the second is the water-gas shift reaction.
The overall reaction is described as follows:
CH
4
+ 2H
2
O CO
2
+ 4H
2
, H = 165 kJ/mol

Since the overall reaction is endothermic, it is necessary to supply the needed
heat to the reaction from combustion of a part of the fuel in a direct-fired or indirectly
fired furnaces. The equilibrium concentrations for first reaction are shifted to the right
at high temperature and low pressure. To achieve an almost complete conversion of
the methane to CO and H
2
, a very high temperature and long residence time at this
high temperature is necessary.

Description of Production of Hydrogen
The first step in the production of synthesis gas is to treat natural gas to remove
hydrogen sulfide. The purified gas is then mixed with steam and introduced to the
first reactor (primary reformer). The reactor is constructed from vertical stainless steel
tubes lined in a refractory furnace. The gas mixture flows from top to bottom through
tubes arranged in vertical rows. While flowing through the tubes heated from the
outside, the hydrocarbon/steam mixture reacts, forming hydrogen and carbon
monoxide in accordance with the following reactions mention in significance of steam
methane reforming (SMR).

A promoted nickel type catalyst contained in the reactor tubes is used at
temperature and pressure ranges of 830 C and 30 bar, respectively. The reforming
reaction is equilibrium limited. It is favored at high temperatures, low pressures, and a
high steam to carbon ratio. These conditions minimize methane slip at the reformer
outlet and yield an equilibrium mixture that is rich in hydrogen.

Operational Problems
Problem 1: Unable to maintain specific temperature of reactor over the time
Cause : Sintering of catalyst
- It leads to loss of active surface and, consequently, a decrease in activity.
Apart from reduced dispersion, also ideally shaped crystallites are formed,
which are generally less reactive.
- It tends to be faster for narrow particle size distributions on the support.
Solution : Make sure there is mixing between hydrogen and natural gas before enters
the reactor

Problem 2: Sulphur poisoning
Cause : Catalyst deactivation
- Poison blocks active surface sites and may change the atomic surface
structure in a way that reduces the catalytic activity.
- Poison also changes the surface structure of nickel. (Somorjai,1972)
Solution : Regeneration of catalyst and make sure the optimum temperature and
pressure of hydrosulfurizer is maintained

Kinetics of Steam methane reforming (SMR) catalyst
According to Xu and Froment(Xu,1989), the kinetic and mechanistic details of steam
methane reforming on a Ni/MgAl
2
O
4
catalyst is shown as follows:
1. H
2
O reacts with surface nickel atoms, yielding adsorbed oxygen and gaseous
hydrogen.
2. The H
2
formed is directly released into the gas phase and/or the gaseous H2 is in
equilibrium with adsorbed H and H2.
3. Methane is adsorbed on surface nickel atoms. The adsorbed methane either reacts
with the adsorbed oxygen or dissociates to form chemisorbed radicals.
4. The adsorbed oxygen and the carbon-containing radicals react to form chemisorbed
CH2O, CHO, CO, or CO
2
.
5. CO and CO
2
are formed out of CHO and CH
2
O species.

The following reaction scheme is shown as follows:
H
2
O + * O* + H
2

CH
4
+ * CH
4
*
CH
4
* + * CH
3
* + H*
CH
3
* + * CH
2
* + H*
CH
2
* + O* CH
2
O* + *
CH
2
O* + * CHO* + H*
CHO* + * CO* + H* (rate-determining step, r.d.s.) (7)
CO* + O* CO
2
* + * (r.d.s.)
CHO* + O* CO
2
* + H* (r.d.s.)
CO* CO + *
CO
2
* CO
2
+ *
2H* H
2
* + *
H
2
* H
2
+ *
The mechanism indicates that reactions of carbon-intermediates with adsorbed
oxygen are rate determining, suggesting that the properties of the oxygen present may
determine to a large extent the reaction kinetics.