44 Gasification Fundamentals

Temperature and pressure measurements of a gasifier can be difficult to obtain. One

may estimate an effective gasification temperature and pressure by measuring the
composition of the syngas, and then calculating the equilibrium conditions that would
create that syngas. From the concentration of H2, H2O, CO, and CO2, one may calculate
the water gas shift equilibrium constant using Equation 3.1. One may then estimate the
gasification temperature using Figure 3.2 or Equation 3.2. An additional measurement of
CH4 concentration allows the pressure to be estimated. Note that the definition of a gas
partial pressure is the mole fraction of that gas, y, times the system pressure. For
component i:
Pi ¼ yi P Eqn. 3.7
This definition may then be substituted into Equation 3.3 to give:

yCO ðyH2 Þ8 p2
KMS ¼ Eqn. 3.8
yCH4 yH2 O

Setting Equation 3.8 equal to Equation 3.4 gives:

yCO ðyH2 Þ3 p2
KMS ¼ ¼ eb P a lnðPÞ
yCH4 yH2 O
 
1
¼ ½b  lnðyCO Þ  3lnðyH2 Þ þ lnðyCH4 Þ þ lnðyH2 O Þ Eqn. 3.9
2a
The constants a and b may be found from the temperature and Equations 3.5
and 3.6.

Example 3.1: Estimating Gasification Temperature and Pressure

based on Gas Composition
Powder River Basin coal was gasified in a Transport Gasifier using an oxygen-enriched
air feed to yield syngas with the following composition:8

mole%
H2 O 27.5
CO 7.65
H2 12.61
CO2 12.77
CH4 1.92
Ar 0.12
N2 37.45
 Gasification Fundamentals 45

The temperature and pressure of the gasifier will be estimated based on the gas compo-
sition. First, the water gas shift equilibrium constant will be calculated using Eqn. 3.1:
PCO2 PH2 yCO2 yH2 ð0:1277Þð0:1261Þ
KWG ¼ ¼ ¼ ¼ 0:76544
PCO PH2 O yCO yH2 O ð0:0765Þð0:275Þ
From Figure 3.2, we can see that the temperature is about 925 oC or 1,198 K. This
approximate solution is useful, as Eqn. 3.2 has multiple roots:
lnðKWG Þ ¼ lnð0:76544Þ ¼ 1:8907½lnðTÞ2  30:084lnðT Þ þ 117:942
This was solved using Solver in Microsoft Excel to find that T equals 1,184 K or
911 oC. Alternatively, we could have solved Eqn. 3.2 using the quadratic equation, and
selected the root that was closest to the estimate based on Figure 3.1.
The pressure can then be estimated using Eqn. 3.9. First, we calculate the temper-
ature-dependent a and b constants from Eqn. 3.5 and Eqn. 3.6:
a ¼ 7:1635ðT=1; 000Þ5 þ 53:378ðT =1; 000Þ4  157:83ðT =1; 000Þ3
þ 230:86ðT =1; 000Þ2  166:32ðT =1; 000Þ þ 44:849
¼ 2:1768

b ¼ 9:5578ðT =1; 000Þ3  52:5ðT =1; 000Þ2 þ 105:19ðT =1; 000Þ  61:45 ¼ 5:4115

Then, using Eqn. 3.9:

 
1
lnðPÞ ¼ ½b  lnðyCO Þ  3lnðyH2 Þ þ lnðyCH4 Þ þ lnðyH2 O Þ ¼ 2:1428
2a

P ¼ e2:1428 ¼ 8:52 MPa

The reported average riser exit temperature was 907 oC; which is very close to the
estimated 911 oC based on the gas composition. The riser exit temperature should be
a little lower than the temperature near the base of the gasifier because of endothermic
reactions in the riser.
On the other hand, the estimated pressure of 8.52 MPa, does not compare well to the
reported pressure of 1.303 MPa. The good temperature prediction shows that the water
gas shift reaction, which is shown in R-3.9, is nearly at equilibrium in the reactor. The
poor pressure prediction shows that methane is formed during gasification and that the
steam methane reforming reaction, shown in R-3.10, is not at equilibrium.
In the high temperature environment of an entrained flow gasifier, the methane
steam reforming reaction is more likely to be near equilibrium. As shown in Figure 3.2,
however, the equilibrium methane concentrations are low, and obtaining an accurate
measure of methane content may be difficult.