Gasification

Reactions:
During the process of gasification of solid carbon, whether in the form of coal, coke or char, the principle
chemical reactions are those involving carbon, carbon monoxide, carbon dioxide, hydrogen, water (or steam)
and methane. These are:
 Combustion reactions,

the Boudouard reaction,

the water gas reaction,

and the methanation reaction,

For real fuels (including coal, which also contains hydrogen), the overall reaction can be written as:
CnHm + n/2O2 → nCO + m/2H2 where
● for gas, as pure methane, m = 4 and n = 1, hence m/n = 4
● for oil, m/n ≈ 2, hence m = 2 and n = 1
● for coal, m/n ≈ 1, hence m = 1 and n = 1.
Gasification Reactors
For gasification processes, reactor types can be grouped into one of three categories: moving-bed gasifiers,
fluid-bed gasifiers, and entrained-flow gasifiers.
Moving-bed gasifiers (sometimes called fixed-bed gasifiers) are characterized by a bed in which the coal moves
slowly downward under gravity as it is gasified by a blast that is generally, but not always, in a counter-current
blast to the coal. In such a counter-current arrangement, the hot synthesis gas from the gasification zone is used
to preheat and pyrolyse the downward flowing coal. With this process the oxygen consumption is very low, but
pyrolysis products are present in the product synthesis gas. The outlet temperature of the synthesis gas is
generally low, even if high, slagging temperatures are reached in the heart of the bed. Moving-bed processes
operate on lump coal. An excessive amount of fines, particularly if the coal has strong caking properties, can
block the passage of the up-flowing syngas.
Fluid-bed gasifiers offer extremely good mixing between feed and oxidant, which promotes both heat and mass
transfer. This ensures an even distribution of material in the bed, and hence a certain amount of only partially
reacted fuel is inevitably removed with the ash. This places a limitation on the carbon conversion of fluid-bed
processes. The operation of fluid-bed gasifiers is generally restricted to temperatures below the softening point
of the ash, since ash slagging will disturb the fluidization of the bed. Some attempts have been made to operate
into the ash-softening zone to promote a limited and controlled agglomeration of ash with the aim of increasing
carbon conversion. Sizing of the particles in the feed is critical; material that is too fine will tend to become
entrained in the syngas and leave the bed overhead. This is usually partially captured in a cyclone and returned
to the bed. The lower temperature operation of fluid-bed processes means that they are more suited for gasifying
reactive feedstocks, such as low-rank coals and biomass.
Entrained-flow gasifiers operate with feed and blast in co-current flow. The residence time in these processes is
short (a few seconds). The feed is ground to a size of 100 µm or less to promote mass transfer and allow
transport in the gas. Given the short residence time, high temperatures are required to ensure a good conversion,
and therefore all entrained-flow gasifiers operate in the slagging range. The high-temperature operation creates
a high oxygen demand for this type of process. Entrained-flow gasifiers do not have any specific technical
limitations on the type of coal used, although coals with a high moisture or ash content will drive the oxygen
consumption to levels where alternative processes may have an economic advantage.
Moving Bed Gasifiers: The Lurgi Gasifier

The heart of the Lurgi process is in the reactor, in which the blast and syngas flow upwards in counter-current to
the coal feedstock. Coal is loaded from an overhead bunker into a lock-hopper that is isolated from the reactor
during loading, then closed, pressurized with syngas, and opened to the reactor. The reactor is thus fed on a
cyclic basis.
The coal from the lock-hopper is distributed over the area of the reactor by a mechanical distribution device,
and then moves slowly down through the bed, undergoing the processes of drying, devolatilization, gasification
and combustion. The ash from the combustion of ungasified char is removed from the reactor chamber via a
rotating grate, and is discharged into an ash lock-hopper. In the grate zone, the ash is precooled by the incoming
blast (oxygen and steam) to about 300–400°C.
The blast enters the reactor at the bottom and is distributed across the bed by the grate. Flowing upward, it is
preheated by the ash before reaching the combustion zone in which oxygen reacts with the char to form CO2. At
this point in the reactor the temperatures reach their highest level. The CO2 and steam then react with the coal in
the gasification zone to form carbon monoxide, hydrogen and methane. The gas composition at the outlet of the
gasification zone is governed by the three heterogeneous gasification reactions: water gas, Boudouard, and
methanation.

This gas leaving the gasification zone then enters the upper zones of the reactor, where the heat of the gas is
used to devolatilize, preheat and dry the incoming coal. In this process the gas is cooled from about 800°C at the
outlet of the gasification zone to about 550°C at the reactor outlet.
A result of the counter-current flow is the relatively high methane content of the outlet gas. On the other hand,
part of the products of devolatilization are contained unreacted in the synthesis gas, particularly tars, phenols
and ammonia, but also a wide spread of other hydrocarbon species. Bulk removal of this material takes place
immediately at the outlet of the reactor by means of a quench cooler in which most of the high-boiling
hydrocarbons and dust carried over from the reactor are condensed and/or washed out with gas liquor from the
downstream condensation stage.
Fluid-Bed Processes
In fluid-bed gasification processes the blast has two functions: that of blast as a reactant and that of the
fluidizing medium for the bed. Common issues related to process are:
 Operating temperature
 Feed quality
 Carbon conversion
 Ash
  Equipment issue
The Winkler process
The Winkler atmospheric fluid-bed process was the first modern continuous gasification process using oxygen
rather than air as blast. The Winkler process is operable with practically any fuel. Coal preparation requires
milling to a particle size below 10 mm, but does not require drying if the moisture content is below 10%. The
feed is conveyed into the gasifier or generator by a screw conveyor. The fluid bed is maintained by the blast,
which enters the reactor via a conical grate area at the base. An additional amount of blast is fed in above the
bed to assist gasification of small, entrained coal particles. This also raises the temperature above that of the bed
itself, thus reducing the tar content of the syngas. The reactor itself is refractory lined. Operation temperature is
maintained below the ash melting point – most commercial plants have operated between 950 and 1050°C. At
maximum load, the gas velocity in a Winkler generator is about 5 m/s. The flow sheet incorporates a partly
radiant waste heat boiler and a cyclone to remove the ash. The ash contains a considerable amount of unreacted
carbon – over 20% on feed which can be burnt in an auxiliary boiler.
This process is now, however, only of historic interest, since all but one of these plants has now been shut
down, almost entirely for economic reasons.

The High-Temperature Winkler (HTW) process:

The most important development from the original Winkler process is the increase of pressure, which was
demonstrated at 30 bar. The initial focus was on methanol syngas and hydrogen generation for the parallel
development of a hydrogenating gasifier for SNG production. Development goals included raising the pressure
so as to increase output and reduce compression energy, raising operating temperatures so as to improve gas
quality and carbon conversion, and include a solids recycle from the cyclone to the fluidbed as a further
measure to increase carbon conversion.
Circulating Bed process:
The characteristics of a circulating fluidized bed combine many advantages of the stationary fluidized bed and
the transport reactor. The high slip velocities ensure good mixing of gas and solids, and thus promote excellent
heat and mass transfer. Small particles are converted in one pass, or are entrained, separated from the gas, and
returned via an external recycle. Larger particles are consumed more slowly and are recycled internally inside
the bed until they are small enough for external recycling. The CFB operates with a much higher circulation rate
than a classical stationary bed, thus creating a specific advantage in the higher heating rate experienced by the
incoming feed particles. This significantly reduces the tar formation during the heating up process.
The CFB system comprises the reactor, an integral recycle cyclone and a seal pot. The high gas velocities (5–8
m/s) ensure that most of the larger particles are entrained and leave the reactor overhead. The solids separated
from the gas in the cyclone are returned to the reactor via the seal pot. The gasifying agent, usually air, is fed as
primary air through the nozzle grate and, as secondary air, at a level above the fuel supply point. For biomass
applications the fuel must undergo size reduction to 25–50 mm.
Transport bed gasifier:
Fluid-bed gasification has also been developed in the high velocity regime. Such a gasifier is the Kellogg
Brown and Root (KBR) transport gasifier for which a gas velocity in the riser of 11–18 m/s is reported. The
objective of this development was to demonstrate higher circulation rates, velocities and riser densities than in
conventional circulating beds, resulting in higher throughput and better mixing and heat transfer rates. The fuel
and sorbent (limestone for sulfur removal) are fed to the reactor through separate lock-hoppers. They are mixed
in the mixing zone with oxidant and steam, and with recirculated solids from the standpipe. The gas with
entrained solids moves up from the mixing zone into the riser. The riser outlet makes two turns before entering
the disengager, where larger particles are removed by gravity separation. Smaller particles are largely removed
from the gas in the cyclone. The solids collected by the disengager and cyclone are recycled to the mixing zone
via the standpipe and J-leg. The gas is cooled in a syngas cooler prior to fine particulate removal in a candle
filter. The sorbent added to the fuel reacts with the sulfur present to form CaS. Together with a char–ash
mixture, this leaves the reactor from the standpipe via a screw cooler. These solids and the fines from the candle
filter are combusted in an atmospheric fluid-bed combustor.