Water Gas Shift Reactor (WGS)

The WGSR is an important industrial reaction that is used in the manufacture of ammonia,
hydrocarbons, methanol, and hydrogen. It is also often used in conjunction with steam
reformation of methane and other hydrocarbons. In the FischerTropsch process, the WGSR is
one of the most important reactions used to balance the H
2
/CO ratio. It provides a source of
hydrogen at the expense of carbon monoxide, which is important for the production of high
purity hydrogen for use in ammonia synthesis.

Water gas shift (WGS) reactors is to convert carbonmonoxide into carbon dioxide,
CO + H2O CO2 + H2, H = - 9.8 kcal/mol

The equilibrium of this reaction shows a significant temperature dependence and the equilibrium
constant decreases with an increase in temperature, that is, higher carbon monoxide conversion is
observed at lower temperatures. In order to take advantage of both the thermodynamics and
kinetics of the reaction, the industrial scale water gas shift reaction is conducted in multiple
adiabatic stages consisting of a high temperature shift (HTS) followed by a low temperature shift
(LTS) with intersystem cooling.
[2]
The initial HTS takes advantage of the high reaction rates, but
is thermodynamically limited, which results in incomplete conversion of carbon monoxide and a
2-4% carbon monoxide exit composition. To shift the equilibrium toward hydrogen production, a
subsequent low temperature shift reactor is employed to produce a carbon monoxide exit
composition of less than 1%. The transition from the HTS to the LTS reactors necessitates
intersystem cooling. Due to the different reaction conditions, different catalysts must be
employed at each stage to ensure optimal activity. The commercial HTS catalyst is the iron
oxidechromium oxide catalyst and the LTS catalyst is a copper-based catalyst. The order
proceeds from high to low temperature due to the susceptibility of the copper catalyst to
poisoning by sulfur that may remain after the steam reformation process.
[3]
This necessitates the
removal of the sulfur compounds prior to the LTS reactor by a guard bed in order to protect the
copper catalyst. Conversely, the iron used in the HTS reaction is generally more robust and
resistant toward poisoning by sulfur compounds. While both the HTS and LTS catalysts are
commercially available, their specific composition varies based on vendor. An important
limitation for the HTS is the H
2
O/CO ratio where low ratios may lead to side reactions such as
the formation of metallic iron, methanation, carbon deposition, and FischerTropsch reaction.
Low temperature shift (LTS)
The typical composition of commercial LTS catalyst has been reported as 32-33% CuO, 34-53%
ZnO, 15-33% Al
2
O
3
.
[3]
The active catalytic species is CuO. The function of ZnO is to provide
structural support as well as prevent the poisoning of copper by sulfur. The Al
2
O
3
prevents
dispersion and pellet shrinkage. The LTS shift reactor operates at a range of 200
o
C to 250
o
C.
Low reaction temperatures must be maintained due to the susceptibility of copper to thermal
sintering. These lower temperatures also reduce the occurrence of side reactions that are
observed in the case of the HTS.Noble metals such as Pt supported on ceria has been extensively
used for LTS
[4]
.
High temperature shift catalysts
The typical composition of commercial HTS catalyst has been reported as 74.2% Fe
2
O
3
, 10.0%
Cr
2
O
3
, 0.2% MgO (remaining percentage attributed to volatile components).
[5]
The chromium
acts to stabilize the iron oxide and prevents sintering. The operation of HTS catalysts occurs
within the temperature range of 310
o
C to 450
o
C. The temperature increases along the length of
the reactor due to the exothermic nature of the reaction. As such, the inlet temperature is
maintained at 350
o
C to prevent the exit temperature from exceeding 550
o
C. Industrial reactors
operate at a range from atmospheric pressure to 8375 kPa.
[5]

Both WGS stages have superficial contact times greater than 1 s. Based on journal, the
WGS reaction is supposed to be complete at a temperature of 400
o
C. Therefore, on our power
plant project will use the typical high temperature shift catalysts (HTS) which has been described
above.