Materials of Construction in Partial Oxidation

Operating conditions in partial oxidation reactors and steam

reformers vary

considerably - depending on the feedstock that is being used. An

operating

temperature of 1400°C (i.e., the temperature of the inner surface of

the lining) is

not critical for many refractory materials. However factors other than

temperature determine the refractory selection and the refractory

design.

The partial oxidation process CO and hydrogen - strongly reducing

gasses

that are able to reduce free silica if it is present in the hot face bricks. This
results in a more porous structure of the brick and an increased surface for the
reaction with slags. In addition, the volatile silica leaves the reactor with the gas
stream and can be deposited inside the boiler tubes where it increases the
potential to plug the tubes. Therefore, a low percentage of silica in bricks is
required (i.e., a maximum of 0.25%). The presence of vanadium pentoxide
in the slags also causes severe chemical attack on the refractory181.
The refractory lining in partial oxidation reactors is usually composed of
dense brick at the hot face and various refractory insulating materials (insulating
bricks, castables and other products) between the inner layer of dense bricks and
the steel shell. The design of the refractory lining should provide close
dimensional tolerances between the bricks. Open joints in the brickwork may
cause by-passing and/or slag penetration. Because the reactors are heated up
and cooled down fairly frequently during commissioning of the plant, the
refractory materials should have sufficient volume stability and thermal shock
resistance to accommodate these extreme temperature fluctuations 81.
The production of high-pressure steam by cooling syngas creates the
potential for metal dusting. The term “metal dusting” refers to the situation in
which a metal surface in contact with carbon monoxide turns to powder. This
takes place under certain process conditions in which carbon diffuses into a
metal matrix and forms carbides. These carbide formations result in a buildup
of stress that causes metal dusting177.
The potential for carbon formation is based on the gas composition and
metal temperature. Industry experience shows that if the gas temperature is less
than ~1100°F, the kinetics of the reaction are too low and carbon does not form.
The equilibrium Kp for typical gasifier reactor effluent compositions is about
1800°F. If the calculated Kp, which is based on gas composition, is greater than
the equilibrium Kp, carbon cannot form. Therefore, gasifier reactor effluent
metal dusting potential typically occurs between the temperatures of 1100°F and
1800°F.
For metal dusting to occur in the gasifier reactor effluent, two essential
elements are necessary: 1) a metal surface and 2) a metal surface temperature
between 1100°F and 1800°F (595 to 895°C). The temperature of syngas leaving
the gasification reactor passes through this temperature range. With the piping
and equipment providing a metal surface, the remaining element necessary for
metal dusting is the metal surface temperature177