C3M Theory Documentation

Table of Contents
1.

Moisture Release ..................................................................................................................... 3

1.1

Mass Balance.................................................................................................................... 3

1.2

MGAS .............................................................................................................................. 3

1.2.1

2.

1.3

PCCL ................................................................................................................................ 3

1.4

Physical Properties ........................................................................................................... 3

Pyrolysis .................................................................................................................................. 4
2.1

Primary Pyrolysis ............................................................................................................. 4

2.1.1

Mass Balance ............................................................................................................ 4

2.1.2

Obtaining FC_m from Pyrolysis Sub-Models .......................................................... 6

2.1.3

and Coefficients (Stoichiometry) ....................................................................... 7

2.1.4

Chemical Rates ....................................................................................................... 10

2.1.5

Physical Properties of Volatile Matter and Tar....................................................... 12

2.2

Secondary Pyrolysis ....................................................................................................... 13

2.2.1

Mass Balance .......................................................................................................... 13

2.2.2

Beta Coefficients (Stoichiometry) .......................................................................... 13

2.2.3

Physical Properties of Soot ..................................................................................... 14

2.2.4

Chemical Rates ....................................................................................................... 14

2.3

3.

Chemical Rate ........................................................................................................... 3

Tar Cracking................................................................................................................... 15

2.3.1

MGAS ..................................................................................................................... 15

2.3.2

PCCL....................................................................................................................... 15

2.3.3

Beta Coefficients (Stoichiometry) .......................................................................... 15

2.3.4

Physical Properties of PAH and Oil........................................................................ 16

Gasification ........................................................................................................................... 16
3.1

Char Gasification............................................................................................................ 16

3.1.1

MGAS ..................................................................................................................... 16

3.1.2

PCCL....................................................................................................................... 17

3.2

Soot Gasification ............................................................................................................ 19

3.2.1

Steam Gasification .................................................................................................. 19

3.2.2

CO2 Gasification ..................................................................................................... 19

1

4.

3.2.3

Methanation ............................................................................................................ 19

3.2.4

PCCL Constants ...................................................................................................... 19

3.2.5

Choosing PCCL Gas Environment ......................................................................... 20

Oxidation............................................................................................................................... 20
4.1

4.1.1

Mass Balance .......................................................................................................... 20

4.1.2

Chemical Rates ....................................................................................................... 21

4.2

Mass Balance .......................................................................................................... 21

4.2.2

Chemical Rates ....................................................................................................... 21

Mass Balance .......................................................................................................... 22

4.3.2

Chemical Rate ......................................................................................................... 22

CO Combustion .............................................................................................................. 24

4.4.1

Mass Balance .......................................................................................................... 24

4.4.2

Chemical Rate ......................................................................................................... 24

4.5

H2 Combustion ............................................................................................................... 24

4.5.1

Mass Balance .......................................................................................................... 24

4.5.2

Chemical Rate ......................................................................................................... 25

4.6

CH4 Combustion ............................................................................................................ 25

4.6.1

Mass Balance .......................................................................................................... 25

4.6.2

Chemical Rate ......................................................................................................... 25

4.7

7.

Char Oxidation ............................................................................................................... 22

4.3.1
4.4

6.

Soot Oxidation................................................................................................................ 21

4.2.1
4.3

5.

Tar Oxidation ................................................................................................................. 20

Higher Hydrocarbon Combustion .................................................................................. 25

4.7.1

Mass Balance .......................................................................................................... 25

4.7.2

Chemical Rate ......................................................................................................... 25

Water Gas Shift ..................................................................................................................... 26

5.1

Mass Balance.................................................................................................................. 26

5.2

Chemical Rate ................................................................................................................ 26

Methods for Estimating Thermodynamic Properties of Pseudo Species .............................. 26

6.1

Estimation of Heats of Formation for CHNOS Compounds.......................................... 26

6.2

Estimation of Specific Heat of CHONS compounds ..................................................... 27

Surrogate Modeling .............................................................................................................. 30

1. Moisture Release
Two sub-models handle moisture release in C3M: MGAS and PCCL.

1.1

Mass Balance

The chemical reaction is simply a phase change as shown in Eq. (1.1).

1.2

2 2

MGAS

(1.1)

Moisture release through MGAS is handled in an Arrhenius equation form. There are more
realistic ways to handle moisture release such as thermodynamic equilibrium. However, the
equation in MGAS has been shown to be stable in most all CFD simulations. Problems arise if
the rate is too quick compared to the cell size and time step. Very quick rates can cause the
pressure solver to fail in some cases. The MGAS rate is fast enough to be realistic, but slow
enough to prevent pressure solver failure.
1.2.1
Chemical Rate
The rate expression comes from the MGAS Manual.[1]
=

exp

(1.2)

Here, kd and Ead are kinetic parameters from the MGAS model, R is the universal gas constant
defined in J/mol/K, Ts is the local solids temperature in K, s is the local solids volume fraction,
s is the local solids density, and 2 is the local mass fraction of the moisture in the coal.

1.3

PCCL

The moisture release in PCCL is handled via heat transfer limitations. A calculation is done
within PCCL to estimate the amount of heat being transferred to the coal. This heat is assumed
to go into the vaporization of water until it is gone rather than raising the temperature of the
particle. If this assumption is true and if the reactor environment temperature remains
approximately constant during the moisture release, the rate of heat transfer will be constant and
thus the moisture release rate is constant. PCCL specifies the moisture release rate in kg/m2/s in
CFDC1T1.RPT under the DRYING RATE section. The flux specified in the report is taken
as Fm. The total flux on a mass per cell volume basis in kg /m3/s is given in Eq. (1.3) when dp is
in meters.
6

= 2
(1.3)
0

Here s is the local solids volume fraction, and dp is the particle diameter in meters, Ts is the local
solids temperature in K. The full implementation of the rate expression includes switches such
that the rate isnt turned on until the solids temperature reaches the saturation temperature of
water. The saturation temperature of water is based on the Antoine equation for water.

1.4

Physical Properties

The moisture in the coal is modeled as if it were pure water in the liquid state. The moisture in
the gas phase is modeled as pure moisture in the gas phase.
3

2. Pyrolysis
Pyrolysis is the process of thermal decomposition of a fuel that does not involve the consumption
of any gas species. In C3M, there are three pyrolysis reactions: Primary Pyrolysis, Secondary
Pyrolysis, and Tar Cracking. At lower temperatures (under 1000oC) it is thought that primary
pyrolysis occurs along with tar cracking. Primary pyrolysis results in the formation of light
gases and tar which may be allowed to subsequently crack to form further light gases. At
temperatures above 1000oC, the secondary pyrolysis mechanism is thought to occur in which any
tar formed is converted to soot and light gases.

2.1

Primary Pyrolysis

Primary pyrolysis is the thermal decomposition of volatile matter to form light gases and tar.
These reactions generally occur at temperatures under 1000oC. If the reactor generally operates
above 1000oC, one should use the Secondary Pyrolysis outlined in Section 2.2.
2.1.1
Mass Balance
The mass of all elements in C3M is carefully maintained within C3M such that the amount of
each element defined in the ultimate analysis is conserved. However, the amount of fixed carbon
and volatile matter defined in the proximate analysis of the coal can shift depending on the
specific pyrolysis conditions. The reason for this is that the ASTM method used to determine the
proximate analysis has a prescribed heating profile.[2] While this is useful for comparing coals, it
is not useful in determining the volatile content under differing conditions than the standard test.
Computer codes such as PCCL, FG-DVC, and CPD can predict the volatile mass content and
species distribution. The proximate analysis is thus adjusted to account for this change in C3M.
The fixed carbon content must be reported by any sub-model used for devolatilization. Once this
value is determined, an adjusted proximate analysis is determined and the composition of the
volatile mater and tar is determined. The carbon, hydrogen, oxygen, nitrogen, and sulfur from
the ultimate analysis (UA) are referred to as UAC, UAH, UAO, UAN, and UAS respectively.
These values never change. Similarly, the ash and moisture content of the as received
proximate analysis (PA) are steady and referred to as PAA and PAM respectively. The fixed
carbon and the volatile matter from any of the devolatilization models are referred to as FC_m
and VM_m. The adjusted fixed carbon of the proximate analysis are referred to as PAFC_adj,
and the volatile mater as PAVM_adj. All of these quantities are mass fractions.
In C3M, it is assumed that PAFC_adj is pure carbon, and the sum of PAFC_adj, PAVM_adj,
PAM, and PAA is one. The FC_m taken from the sub-model is the mass fraction of pure carbon
in the char on a dry ash free basis such that Eq (2.1) is satisfied.
_ + _ = 1

(2.1)

A sub-model may report other elements in the char such as oxygen, nitrogen, hydrogen, and
sulfur. However, these elements are assumed to go to the volatile mater and/or tar during any
reactions because char is pure carbon in C3M reactions.

Once FC_m is determined, the proximate analysis is adjusted according to Eqs (2.2) and (2.3).
_ = _(1 )

_ = 1 _adj

(2.2)
(2.3)
4

The adjusted proximate analysis parameters represent the mass fractions of coal that will end up
as char (carbon), volatiles, water, and ash during any subsequent reaction steps. Therefore, the
composition of the volatile mater is determined by difference. The ultimate analysis numbers
used are defined on a DAF basis. If they are not defined that way, they are converted. Because
the fixed carbon is assumed to be pure carbon, the elemental mass fractions of the volatile matter
are defined in terms of the ultimate analysis and the reported carbon content from the
devolatilization model.
=

_
(1_)

= (1_)

= (1_)

= (1_)

= (1_)

(2.4)

(2.5)
(2.6)

(2.7)
(2.8)

The elemental composition of the tar is defined based on the devolatilization reaction and the
Alpha/Beta coefficients reported by C3M. The determination of the Beta coefficients from each
sub model is explained in Section 2.1.3.
The generalized devolatilization model in C3M is expressed as a reaction in mass terms.
+ + 2 2 + 4 4 + 2 2 + 2 2 + +
2 2 + 3 3 + 2 4 2 4 + 2 6 2 6 + 3 6 3 6 + 3 8 3 8

(2.9)

A sub-model may report many more species than these for primary pyrolysis, but the mass is
combined such that only tar, CO, CO2, CH4, H2, H2O, H2S, NH3, C2H2, C2H6, C3H8, and C6H6
are generated. It is assumed that one gram of volatile mater breaks up into the mass fractions
from the and s. The sum of and all the coefficients is thus one.
The elemental mass fraction of tar are defined as follows (equivalent to an ultimate analysis):
=

+2
+4
+2 4
2 4 +2 6 2 6 +3 8 3 8 +3 6 3 6 +
2
4

4
+2 +2
+24 2 4 +26 2 6 +38 3 8 +36 3 6 + +
2

4
2
2

+2
+2

2
2

3
+

3

(2.10)
(2.11)
(2.12)
(2.13)
(2.14)

Here is the mass ratio of element A in molecule B and is calculated based on the number of
atoms (x) of element A in molecule B times the ratio of the atomic weight (AW) of A to the
molecular weight (MW) of B.

(2.15)

It should be noted that if any of the Tar mass fractions become negative, it is a clear indication
that there was a failure in the mass balance due to the way the coefficients were calculated.
This most likely indicates that the sub-model did not converge on a solution.
The molecular weight of tar and volatile matter (MWTar and MWVM respectively) are either
assumed or defined by the sub model. Their values are somewhat arbitrary as long as they are
consistently used throughout the C3M model. The molecular weight of tar does effect the
volume of gas it takes up and the volume of gas generated when the material is combusted. A
high molecular weight compound consumes a small volume but releases a large volume of gas
when combusted. This is an important thing to keep in mind which can cause solvers to fail if
the rates of combustion are fast.
The conversion of Eq. (2.9) from mass units to molar units is defined where n is the
stoichiometric coefficient in moles.
=

(2.16)

= , , , 2 , 4 , 2 , 2 , 2 , 3 , 2 2 , 2 6 , 3 8 , 6 6 ; = 1; =

Using this procedure for any devolatilization model within C3M ensures that total mass and
element mass are conserved through the primary pyrolysis.
2.1.1.1
Proximate and Ultimate Analysis for Coal/Biomass Mixtures
The proximate and ultimate analysis for coal-biomass mixtures is calculated using a simple
linear blend based on the mass fraction of biomass added.
= + (1 )

(2.17)

Here MF stands for any of mass fractions in the ultimate and proximate analysis. The subscript
B refers to biomass, the subscript C refers to coal, CB refers to the coal/biomass mixture, and X
is the mass fraction of biomass in the mixture.

2.1.2
Obtaining FC_m from Pyrolysis Sub-Models
This section explains how FC_m is obtained from the various sub-models for pyrolysis in C3M.
2.1.2.1
MGAS
In MGAS, the FC_m is simply the fixed carbon from the as received proximate analysis on a
DAF basis.

_ = (1)

(2.18)

In this way, the adjusted proximate analysis is exactly the same as the as received analysis, say
from an ASTM test.

2.1.2.2
PCCL
C3M runs PCCL through an API. The input and output are set as text files and read between the
programs. PCCL outputs a file FDC1CC1.RPT which contains information about the char
yield and its composition. The char yield (Ychar) is reported in column 4 of the table in the file
6

and the carbon content (PCTC) is reported in column 5. Both values are reported as mass
percentages on a DAF basis and the FC_m value is calculated as in Eq. (2.19).
_ =

100

100

(2.19)

PCCL does report char having hydrogen, oxygen, nitrogen, and sulfur. However, because
C3M defines char as 100% carbon, these elements have to report to the tar to prevent an
elemental mass balance problem.

2.1.2.3
CPD
C3M runs CPD internally and reports the outputs in files labled cpd_c3m_outX.txt where x is
1, 2, 3, or 4. cpd_c3m_out1.txt contains a summary of the model output. The last line in the
fsolid column reports the mass fraction of the solids at the final time in the simulated
pyrolysis. This value is taken as the FC_m value.
2.1.2.4
FG-DVC
FG-DVC is called by C3M and run via input files and it generates output files. The summary is
stored in output.txt. The char yield percentage (Ychar) and percentage of carbon (PCTC) are
reported in the COMPOSITION OF DEVOLATILIZATION PRODUCTS section. Eq. (2.19)
is used to calculate FC_m in the same way as PCCL.
2.1.2.5
NETL HPTR Experiments
The NETL HPTR experiments report the mass fraction of products on a dry basis. Char is also
reported on this bases. However, this reported char is the mass of fixed carbon plus the ash.
Since the char is reported on a dry basis, the ash amount reported in the proximate analysis
(which is a wet basis) is used to obtain the amount of carbon.

= (1

(2.20)

Here, the subscript CB refers to the coal/biomass mixture and is calculated according to Eq.
(2.17). By difference, the FC_m value is calculated.
_ =

YChar is calculated by C3M from experimental fits as in Section 2.1.3.5.

(2.21)

2.1.3
and Coefficients (Stoichiometry)
The and coefficients for primary pyrolysis are the mass fractions of tar and light gases
formed during primary pyrolysis from one gram of volatile matter. The names for these
coefficients came from the MGAS manual and have endured through many C3M iterations.
These coefficients represent the mass fractions of species formed from one gram of reactant
(volatiles) and often have a subscript d for devolatilization (a synonym for what we now refer
to as Primary Pyrolysis). This subscript differentiates the alpha and beta coefficients from other
reactions. Eq. (2.9) contains many more beta coefficients than are typically used. The following
defines how C3M does the calculations to obtain the coefficients for each sub-model.
2.1.3.1
MGAS
The user is referred to Section 3.1 of the METC Gasifier Advanced Simulation (MGAS)
Model.[1] A detailed explanation of how one is to calculate the mass-based stoichiometric
coefficients are calculated in the MGAS model based on an ultimate and proximate analysis.
7

However, it is worth noting that MGAS will always predict tar to have an ultimate analysis of
0.9 C, 0.08 H, and 0.02 O. Further, it is assumed that any sulfur in the coal ends up as H2S and
any nitrogen ends up as NH3. The remaining product distribution is set to maintain elemental
balance.
2.1.3.2
PCCL
PCCL will predict the DAF mass yields of CH4, C2H4, C2H6, C3H6, C3H8, H2, H2S, CO2, H2O,
CO, HCN, Char and Tar independently. It will also give an ultimate analysis of the Char.
Because of the way C3M works, the char yield is taken as the amount of carbon in the char as
defined in Section 2.1.1. The mass fractions of CO2, H2O, and CO are preserved. The and
coefficients are defined as follows:
=

( )

100(1_)

(2.22)

MFi stands for the mass fraction of species i as defined by PCCL. The values for CH4, C2H4,
C2H6, C3H6, C3H8, H2, H2S are found in the last row of the table in FDC1HC1.RPT, columns 5
to 11. The yields of CO2, H2O, CO, and HCN are found in FDC1NG1.RPT in the last row of
the table in columns 5 to 7, and 9 respectively. All other coefficients are set to zero.
The mass fraction of tar is then defined by difference.
= 1

(2.23)

By this definition, tar contains the balance of all of the H, O, N, and S that was predicted to be in
the char by PCCL. This is a decent simplifying assumption because the mass fraction of carbon
in the char predicted by PCCL is usually ~0.98 or more.
2.1.3.3

CPD

CPD reports mass fractions of solids, H2O, CO2, CH4, CO, Tar, and other. The mass fraction
of other is the combined fractions of light hydrocarbons not heavy enough to be considered tar.
The mass fractions of H2O, CO2, CH4, CO, and other can be found in the last row of the table
in cpd_c3m_out4.txt in the columns marked fh2o, fco2, fch4, fco, and fother. The mass
fractions of tar and solid can be found in the last line of the table in cpd_c3m_out1.txt in the
columns marked ftar and fsolid. As stated in section 2, the DAF carbon content is taken as
fsolid. With these values, it is possible to define the alpha and beta coefficients.
(4)

4 = (1)
(2)

2 = (1)
(2)

(2.24)
(2.25)

2 = (1)

(2.26)

(+)

(2.28)

()

= (1)

(1)

(2.27)

All other s are set to zero. Notice that there is not for H2. This is because CPD does not
explicitly predict hydrogen, but rolls it up in the other fraction with higher hydrocarbons.
Because of this, it is not possible to extract the mass fraction of hydrogen.
2.1.3.4
FG-DVC
The output of FG-DVC is saved in a file called gasyield.txt. FG-DVC will predict yields of
char, H2O, Tar, CO, CO2, CH4, C2H4, HCN, NH3, SO2, COS, CS2, H2S, olefins, and paraffins.
The column variables are titled Char+Ash, H2O-Yld, CO-Yld, CH4-Yld, C2H4-Yld, HCN-Yld,
SO2-Yld, COS-Yld, CS2-Yld, H2S-Yld, Olef-Yld, and Parf-Yld. For brevity, the +Ash and Yld parts of the variable names are neglected from now on. The values used in C3M are taken
from the last line of the table. Hydrogen is not reported but is the balance of what remains. The
Char value given in this table is not pure carbon, but a mix. Even though the column name is
given as Char+ash, there is no ash in the char and the char is an elemental mix of C, H, O, N, and
S. Thus, the FC_m value defined in Section 2.1.2 is also needed. The beta coefficients can then
be defined.
2 =

(100224243222)

4 =

100(1_)

2 4 =
2 =

2 =

(4)

100(1_)
(24)

100(1_)
(2)

100(1_)
(2)

100(1_)
()

= 100(1_)

=
2 =

3 =

()

100(1_)
(2 )

100(1_)
(3 )

100(1_)

All other s are set to zero. The tar can be determined by difference.
= 1 4 24 2 2 2 2 3

(2.29)
(2.30)
(2.31)

(2.32)
(2.33)
(2.34)
(2.35)

(2.36)
(2.37)

(2.38)

Implicit in Eq. (2.38) is that tar contains all of the nitrogen and sulfur compounds as well as the
olefins and paraffins.

2.1.3.5
NETL HPTR Experiments
The model fit of the HPTR data gives yields of Char (which includes Ash), CO2, CO, CH4, H2,
C2H4, and H2O reported as mass fractions. The mass fractions are calculated from Eq. (2.39) and
Table 2-1.
= 0 + + + + 2 + 2

(2.39)
9

Table 2-1: Product Distribution Coefficients for Eq. (2.39)

a0

aX

aXX

aT

aXT

aXXT

Char

6.15E-01

-8.01E-02

-3.99E-01

-1.35E-04

-5.30E-04

6.24E-04

CO2
CO

5.65E-02
-1.21E-01

1.30E-01
-4.38E-01

7.91E-02
-2.98E-03

3.52E-05
2.73E-04

-1.24E-04
7.85E-04

-7.90E-05
5.78E-05

CH4

-2.05E-02

-5.94E-02

-2.36E-02

4.84E-05

9.25E-05

5.18E-05

H2

-2.49E-02

2.49E-03

3.84E-03

4.29E-05

-7.48E-06

-3.70E-06

C2H4

-2.46E-02

-2.32E-02

-4.51E-02

4.86E-05

3.75E-05

8.52E-05

H2O

1.68E-01

-4.89E-02

9.82E-02

-1.03E-04

8.17E-05

-1.12E-04

The tar is calculated by difference as in Eq. (2.40).

= 1

(2.40)

Here X is the biomass mass fraction in the mixture and T is the ultimate temperature of the solids
in oC. This is usually taken as the average temperature in the reactor. The experiments were
conducted between 600 and 975oC and temperatures outside this range should not be used.
The Yi values from Eq. (2.40) are on a dry, ash laden basis and need to be converted to DAF
basis.
=

(1 )

= 1

(2.41)

(2.42)

Char and ash are assumed to be part of the coal that is separate from the volatile mater, so the
reported mass fractions have to be normalized to a weight that does not include the char and ash.
These weighted fractions are the coefficients for pyrolysis.

= (1

Here the subscript i is any of the gas species in Table 2-1.

(2.43)

To convert from the mass based coefficients to mol based stoichiometry, Eq. (2.44) is applied.
=

(2.44)

2.1.4
Chemical Rates
Recent research has shown that the rate at which pyrolysis takes place is relatively
inconsequential to the over-all output in most large scale gasifiers with significant residence time
such as TRIG reactors. However, the product distribution has been shown to be important. That
said, the rate is important if features in the near field of the fuel injectors are important and/or if
the residence time is relatively short as with high temperature entrained flow gasifiers.
There are three equation forms used in C3M for primary pyrolysis. The first follows the form
derived in the MGAS Manual [1] and is referred to as the Two Parameter, Single Stage Model

10

(2P1SM). The second model is the nth Order Arrhenius. The nth Order Arrhenius model is fit to
time-gas evolution data that can come from either a computational sub-model such as CPD or
FG-DVC or experimental TGA data. The third is used for the NETL HPTR Experimental Model
(NHEM).
2.1.4.1
Two Parameter, Single Stage Model (2P1SM)
The 2P1SM is a modified Arrhenius form with a switch based on temperature that accounts for
the amount of volatiles that will remain in the coal if the solids are not heated high enough to
complete the devolatilization.
=

( )/

<

0
0 )
= (
+

867.2 3.914

273
100

<1223
1223

(2.45)
(2.46)
(2.47)

Here, rd is the chemical reaction rate in grams VM/cm3/s, A is the turnover frequency, Ea is the
activation energy, Ts is the solids temperature in K, s is the local volume fraction of the solids,
s is the local true density of the solids in g/cm3, and X denotes mass fraction. The subscripts
VM and FC denote reference to volatile matter and fixed carbon respectively. The superscript 0
denotes reference to the initial values within the fuel (i.e. the adjusted proximate values of the
coal). R is the universal gas constant defined in terms of cal/mol/K.
Note: not all CFD codes will allow a practitioner to define a switch in the chemical rate
definitions. For those codes, it is recommended that Ts in Eq. (2.47) be set to the average
expected operating temperature within the reactor.

The turnover frequency and activation energy are specified by C3M. This equation form is used
for the MGAS and PCCL sub-models. The parameters for the MGAS model are specified in
tables within the MGAS Manual [1]. The parameters for PCCL are read from the
CFDC1T1.RPT file under the DEVOLATILIZATION PRODUCTS & RATE section with
the label of SFOR Pars: and the X* parameter is set to zero.
2.1.4.2
nth Order Arrhenius Model
The nth Order Arrhenius model is used for CPD, FG-DVC, and experimental data determined by
TGA. The equation form is shown in Eq. (2.48).

0
(1)

(2.48)

There are three parameters in this model: A, Ea, and n. The parameter values are determined
through a process of least squared error fits to TGA type data. is the conversion of volatile
matter. The fitting process is done numerically and involves minimizing the numerical integral
of Eq. (2.48) for a single particle.

11

2.1.4.3
NETL HPTR Experimental Model (NHEM)
The NHEM kinetics are based on a the nth order Arrhenius kinetic model as shown in Eq. (2.49).

(1 )

(2.49)

Here, is conversion and t is time. ACB and EaCB are defined in Eq. (2.50) and (2.51) as well as
in Table 2-2. However, the preexponential factor and activation energy are not constants, but
based on the fraction of biomass added to the fuel mix.
= 0 + 1 + 2 2

(2.50)

= 0 + 1 + 2 2

Table 2-2: Coefficients for Kinetic Parameters of Eqs. (2.50) and (2.51)

(2.51)

a0
a1
a2
ACB[1/s]
5.607 -10.16 29.05
EaCB [kJ/mol] 19.62 -7.190 19.45

Noting the following:

=
Eq. (2.49) becomes:
=

(2.52)

1 = 0
0

(2.53)

0


/

(2.54)

Here, rd is the chemical reaction rate in grams of VM/cm3/s, ACB is the turnover frequency, EaCB
is the activation energy, Ts is the local solids temperature in K, s is the local volume fraction of
the solids, s is the local true density of the solids in g/cm3, and denotes the local mass
0
fraction of the volatile matter in the solid phase, and
denotes the mass fraction of the
volatile matter in the coal.

With n=1 in Eq. (2.54) and X*=0 in Eq. (2.46), the NHEM reaction form is equivalent to the
simple Arrhenius in Section 2.1.4.1. However, it is best practice not to assume that n=1 until the
data proves it. Therefore, the most general form of the NHEM is used in C3M as shown in Eq.
(2.54). The data produced in the study of PRB with woody biomass in Table 2-1 and Table 2-2
resulted in a reaction order of unity. However, other data added in future work may not.
2.1.5
2.1.5.1

Physical Properties of Volatile Matter and Tar

Molecular Weights

2.1.5.1.1
MGAS
In MGAS the molecular weights are fixed at 56 g/mol for volatile mater and 144 g/mol for tar.

12

2.1.5.1.2
PCCL
PCCL will report a molecular weight for tar in the FC1YC1.RPT document in column 5 of the
table. The last value in that column is taken as the molecular weight of the tar. The molecular
weight of the volatile mater is reported in CFDC1T1.RPT. This value is used in C3M.
2.1.5.1.3
CPD
CPD reports the molecular weight of tar in the cpd_c3m_out3.txt in column 3. The last value
in that column is taken as the molecular weight of tar. Volatile matter molecular weight is not
reported. As such, it is assumed to be 56 g/mol.
2.1.5.1.4
FGDVC
FG-DVC reports the average molecular weight of both tar and volatile matter in the output.txt
file near the bottom of the file just above the RESULTS OF PERC-VAP MODEL section.
The values reported there are taken as the values within C3M.
2.1.5.1.5
NHEM
The molecular weights in NHEM are assumed to be the same as those in MGAS.
2.1.5.2
Thermodynamic Properties
Volatile matter and Tar are treated like CHONS compounds and properties are calculated
according to section 6.

2.2

Secondary Pyrolysis

At temperatures above 1000oC, tar is known to pyrolize to become a mixture of soot and light
gases. Strictly speaking, the reaction mechanism is complex involving tar and PAH. However,
PCCL handles the kinetics as if volatile matter breaks down in to the combined products of
primary pyrolysis and tar pyrolysis rather than describing all the secondary reactions that take
place. PCCL is the only computational sub-model within C3M that will predict secondary
pyrolysis.
2.2.1
Mass Balance
The over-all reaction is given in Eq. (2.55).
+4 4 +2 2 2 2 +2 2 + +2 2
+2 2 + +2 2

(2.55)

The composition of the volatile matter is calculated the same way as in Section 2.1.1 with Eqs.
(2.4) to (2.8). FC_m is calculated the same way as in Eq. (2.19).
2.2.2
Beta Coefficients (Stoichiometry)
The coefficients in Eq. (2.55) are calculated in much the same way as Section 2.1.3.2. The
mass fractions for secondary pyrolysis are reported in the last line of FDC1SP1.RPT.
4 =

2 2 =

(4)

100(1_)
(22)

100(1_)
()

= 100(1_)

(2.56)
(2.57)
(2.58)

13

2 =

(2)

100(1_)

22

2 =

2 =

(2.59)
(2.60)
(2.61)

2 =

(2.62)

= 1

(2.64)

4 4 2 2 2 2 2 2 2 2

(2.63)

In this set of equations, the coefficients are defined in Eq. (2.15), VMx refers to the mass
fraction of element x in the volatile mater, AWx symbolizes the atomic weight of element x, and
MWx stands for the molecular weight of molecule x. PCCL does report H2O in its output.
However, it is calculated via Eq. (2.60) because the volatile matter can contain more oxygen than
PCCL would predict because of the way that char is defined. If a sub-model predicts char to
have H, N, O, or S, these compounds are forced to be part of the volatile matter. It is for the
same reasons that HCN, H2S, and H2 are calculated according to Eqs. (2.61), (2.62), and (2.63).
Soot is calculated by difference and because all of the H, O, N, and S have been accounted for in
the volatile matter, the soot is pure carbon.
2.2.3
Physical Properties of Soot
Currently, C3M does not contain any complex models for soot nucleation/growth/agglomeration.
Instead, it is assumed that soot is formed as a fully agglomerated particle with a diameter of 0.8
m. At this size, soot is usually treated as a gas phase constituent because it will follow the fluid
in stokes flow. This is a reasonable approximation for most CFD applications.
2.2.3.1
Molecular Weight
It is assumed that soot has a molecular weight of 300.275 g/mol and that it is pure carbon. This
yields a molecular formula of C25.
2.2.3.2
Specific Heat
The development team has not found any information for thermodynamic properties of coal
derived soot as of yet. In the absence of hard data, it is assumed that the specific heat of soot
follows that of char which can be found in section 6.
2.2.3.3
Heat of Formation
The development team has not found any information for thermodynamic properties of coal
derived soot as of yet. In the absence of hard data, the heat of formation is calculated according
to Section 6.1.
2.2.4
Chemical Rates
It is assumed that the additional reactions that produce soot and more gasses proceed much faster
than the primary pyrolysis reaction. Therefore, the limiting step is assumed to be the primary
pyrolysis rate and the same kinetic rate defined in Section 2.1.4.1 is used for this reaction.

14

2.3

Tar Cracking

In lower temperature gasification (below 1000C), tar does not pyrolize but can crack over the
char to form light gasses and possibly more char. MGAS and PCCL will both predict
stoichiometry and kinetics for tar cracking. The tar produced by each sub-model is different in
composition and in its physical properties. Therefore, it is not advisable to use a different model
for tar cracking than is used for primary pyrolysis.
2.3.1
MGAS
The tar cracking reaction in MGAS is assumed to produce char as well as a mixture of CO, CO2,
CH4, H2 and H2O. The reaction is defined in Eq. (2.65).
+ + 2 2 + 4 4 + 2 2 + 2 2

The reaction rate is defined as:

exp

(2.65)
(2.66)

Here rtc is the rate of tar cracking in grams Tar/cm3/s, g is the local volume fraction of the gas,
g is the local gas density, and XTar is the local mass fraction of tar in the gas phase. The
stoichiometric coefficients (c and cs) are supplied by C3M and are calculated according to
the MGAS Manual [1].
2.3.2
PCCL
The tar cracking reaction in PCCL produces a mixture of PAH, oil, CH4, C2H4, C2H6, C3H6,
C3H8, H2, CO, HCN, H2S, H2O, and CO2. Thus, the chemical equation for PCCL in C3M is
shown in Eq. (2.67). The equation is written in terms of mass with 1g of tar going to a
distribution of products.
+ + 4 4 + 2 4 2 4 + 2 6 2 6 + 3 6 3 6 +

3 8
3 8

+ 2 2 + + + 2 2 + 2 2 + 2 2

(2.67)

2.3.3
Beta Coefficients (Stoichiometry)
The tar cracking reaction is written out in the PCCL output file SFTRC1T1.RPT in the same
mass balance form as Eq. (2.67). Therefore, the coefficients can be taken directly from the
file without any necessary conversions. However, because the tar contains extra H, O, N, and S
from the char, a few adjustments must be made.
=
, 2 , 2 ,

22

2 =

2 =

= 1

(2.68)

(2.69)
(2.70)
(2.71)

(2.72)
15

In the above sets of equations i refers to any of the species in Eq. (2.67), AWx symbolizes the
atomic weight of element x, MWx stands for the molecular weight of molecule x, the coefficients
are defined in Eq. (2.15) and Tarx refers to the mass fraction of element x in the tar and was
defined in Eqs. (2.10) to (2.14).
2.3.4

Physical Properties of PAH and Oil

2.3.4.1
Elemental Composition
Because the balance of O, N, and S are forced into gases in Eqs. (2.68) to (2.72), PAH and oil are
strictly hydrocarbon compounds. By Mass balance we can calculate the hydrogen and carbon
content of the mixture of PAH and oil.
=
=

(2.73)

(2.74)

While the elemental composition for the mixture of PAH and OIL can be calculated, one
cannot robustly calculate the elemental composition for PAH and OIL individually because
without solid information about the composition of one of the pseudospecies, there are too
many degrees of freedom to calculate the composition of the other. Further, pushing all of
the O, H, N, and S into the tar and then into light gases also artificially impacts the
composition of the mix. Thus, the composition of both PAH and OIL is assumed to be the
same.
2.3.4.2

Molecular Weight

PCCL does not report any properties for PAH and Oil in the output files. Therefore, it is
assumed that the molecular weight of PAH is 332.3939 g/mol to be consistent with the
formula given for PAH during hydrogenation in the PCCL Manual (an assumed composition
of C25H16O). Certainly, this is not a generally robust assumption for all PAH. Oil is
assumed to have a molecular weight of 92.1384 g/mol. These values are somewhat
inconsequential as long as they are applied consistently throughout the model.
2.3.4.3
Thermodynamic Properties
The thermodynamic properties are estimated according to section 6. The heat of formation is
estimated using Eqs (6.1) and (6.2). The same method for specific heat estimation for tar is used
for these compounds. This may not be the most robust method, but given the lack of solid
information, it is reasonable.

3. Gasification
3.1

Char Gasification

Both the MGAS and PCCL models provide kinetics for char gasification.
3.1.1
MGAS
The reactions in the original MGAS Manual [1] were equilibrium reactions. The pressures are in
atm, temps are in K, the activation energy is in J/mol, x is the local density of phase x in g/cm3,
x is the local volume fraction of phase x, XChar is the local mass fraction of the char, and MwChar
16

is the molecular weight of the char, XSoot is the local mass fraction of the soot, and MwSoot is the
molecular weight of the soot. Tfilm is the algebraic average of Ts and Tg.
3.1.1.1
Steam Gasification
The forward gasification reaction and kinetics are given by Eqs. (3.1) and (3.2).
+ 2 + 2

(3.1)

The reverse gasification reaction and kinetics are given by Eqs. (3.3) and (3.4).
+ 2 + 2

+135728.123

17.29

(3.2)
(3.3)
(3.4)

The activation energy and pre-exponentials are functions of coal type and are supplied by C3M.
3.1.1.2
CO2 Gasification
The forward gasification reaction and kinetics are given by Eqs. (3.5) and (3.6).
+ 2 2

(3.5)

The reverse gasification reaction and kinetics are given by Eqs. (3.7) and (3.8).

2 + 2

+168616.455

20.92

(3.6)
(3.7)

(3.8)

The activation energy and pre-exponentials are functions of coal type and are supplied by C3M.
3.1.1.3
Methanation
The forward gasification reaction and kinetics are given by Eqs. (3.9) and (3.10).
+ 22 4
8078

= exp

7.087

The reverse gasification reaction and kinetics are given by Eqs. (3.11) and (3.12).

= exp

4 + 2 2

13577.5

0.372

0.5

(3.9)

(3.10)
(3.11)

(3.12)

3.1.2
PCCL
PCCL handles gasification reactions via an irreversible reaction. The equations are all of the
same form, but the activation energy, pre-exponential factor, reaction order, K and the annealing
factor () are calculated by C3M and supplied in the output files. The rate is in mol/s/cm3
defined in terms of char consumption. The pressures are in atm, temps are in Kelvin, the

17

activation energy is in kcal/mol, x is the local density of phase x in g/cm3, x is the local volume
fraction of phase x, XChar is the local mass fraction of the char within phase x, and MwChar is the
molecular weight of the char. Tfilm is the algebraic average of Ts and Tg.
3.1.2.1
Steam Gasification
The chemical reaction is the same as Eq. (3.1), but the rate expression is defined in Eq. (3.13).
= exp

2
(1+ 2 )

(3.13)

3.1.2.2
CO2 Gasification
The chemical reaction is the same as Eq. (3.5), but the rate expression is defined in Eq.(3.14).
=

2
exp

(1+ )

(3.14)

3.1.2.3
Methanation
The chemical reaction is the same as Eq. (3.9), but the rate expression is defined in Eq. (3.15).

= exp

(3.15)

3.1.2.4
PCCL Constants
PCCL reports the constants for char gasification within SNORC1CB1.RPT. The preexponential, Activation Energy, reaction order, and K constants are read directly from this file.
In the background, PCCL calculates the gasification kinetics of a char that does not experience
any annealing. It then compares those kinetics to the calculations of the CBKG model which
accounts for annealing and comes up with an annealing factor which is simply a polynomial
factor based on char conversion that acts as a rate multiplier to speed up or slow down the
gasification rate to account for annealing. PCCL actually supplies two equations, one for char
conversions less than 10% and one for char conversions over 10%. NETL has found that the
annealing factor reported by PCCL is not robust. PCCL most often fails to converge when
calculating this factor often resulting in an annealing factor of zero.

Therefore, NETL has developed a new method of calculating the annealing factor. PCCL does
report the CBKG data as a function of time which allows one to use an optimization routine to fit
a polynomial function of any order to the rate.
C3M allows the user to choose between these annealing factor methods on export. The PCCL
option is nothing more than the factors that PCCL reports. The Factor Fit option is the single
polynomial which has the order specified by the user. The Average is a zero order fit.
3.1.2.5
Choosing PCCL Gas Environment (No Longer Supported)
To run PCCL for gasification, the user has to specify the gas environment. This leads to the
issue of what to choose as a representative environment. In a large scale simulation, the local
gas environment can vary considerably. Therefore, C3M includes the option to calculate the
kinetics for each gasification reaction separately in a way that mimics conditions used in
18

experiments. That is, steam gasification kinetics are done in nearly pure steam, CO2 kinetics are
determined in nearly pure CO2, and methanation kinetics are determined in nearly pure H2. One
must use nearly pure gases because PCCL cannot handle having some of the gases set to a
concentration of zero. The concentrations used are 97% of the determining gas, and 1% of the
other gases.

3.2

Soot Gasification

PCCL predicts the formation of soot during the process of secondary pyrolysis. It is also known
that soot is not inert and will continue to react with gas phase constituents. Soot gasification is
handled through PCCL and taken as a non-reversible reaction in the same way that char
gasification is handled. The rate is in mol/s/cm3 in terms of soot consumption. The pressures are
in atm, temps are in K, and the activation energy is in kcal/mol.
3.2.1
Steam Gasification
Soot is broken down by H2O to form H2 and CO.
+ 252 252 + 25

(3.16)

The equation form for the kinetics for soot gasification is the same as with the char gasification.
= exp

2
(1+ 2 )

3.2.2
CO2 Gasification
In this reaction soot is broken down by CO2 to form CO.

+ 252 50

(3.17)
(3.18)

The equation form for the kinetics for soot gasification is the same as with the char gasification.
=

2
exp
(1+ )

3.2.3
Methanation
In this reaction soot is broken down by H2 to form CH4.

+ 502 254

(3.19)
(3.20)

The equation form for the kinetics for soot gasification is the same as with the char gasification.


2

= exp

(3.21)

3.2.4
PCCL Constants
PCCL reports the constants for soot gasification within SNORC1CB1.RPT. The preexponential, Activation Energy, reaction order, and K constants are read directly from this file.
PCCL reports an annealing factor as a polynomial function of soot conversion. That said, one
cannot readily calculate the soot conversion in CFD so it is somewhat useless. However, the
same method used to fit the char gasification is used to fit the soot gasification to come up with a
zero order Averaged fit which serves as a rate multiplier to achieve the best fit to the kinetic
data calculated by CBKG.

19

3.2.5
Choosing PCCL Gas Environment
To run PCCL for gasification, the user has to specify the gas environment. This leads to the
issue of what to choose as a representative environment. In a large scale simulation, the local
gas environment can vary considerably. Therefore, C3M includes the option to calculate the
kinetics for each gasification reaction separately in a way that mimics conditions used in
experiments. That is, steam gasification kinetics are done in nearly pure steam, CO2 kinetics are
determined in nearly pure CO2, and methanation kinetics are determined in nearly pure H2. One
must use nearly pure gases because PCCL cannot handle having some of the gases set to a
concentration of zero. The concentrations used are 97% of the determining gas, and 1% of the
other gases.

4. Oxidation
Oxidation (aka Combustion) is the class of chemical reactions in which fuels react with oxygen
to form oxides. The reactions are considerably faster than any other reactions and highly
exothermic. Because of this, a stiff chemistry solver should be used in a CFD code if these
reactions are used otherwise an extremely small time step will be needed to produce a stable
solution.

4.1

Tar Oxidation

The tar oxidation reaction is available for tar produced by any sub-model in C3M. The
stoichiometry for the reaction is based on the elemental mass fraction calculated in Eq. (2.10) to
(2.14). The rate is assumed to be the rate for C10H22 from Westbrook and Dryer [3].
4.1.1
Mass Balance
The mass balance is centered on a standard equation.
+ 2 2 2 2 + 2 2 + 3 3 + 2 2

(4.1)

The stoichiometric coefficients (nx) in Eq. (4.1) are expressed in terms of moles where x is the
species. In this equation, any nitrogen was assumed to go to molecular nitrogen rather than NOx
because NOx compounds do not form until the flame temperature reaches about 1800K which is
well above most gasifier temperatures. Furthermore, for ultra-high temperature gasification, one
should incorporate reaction thermodynamics and kinetics for NOx compounds which are
currently not part of C3M.
The stoichiometric coefficients can be calculated from the elemental composition determined in
Section 2.1.1.
2 =

2 =
3 =
2 =

(4.2)

(4.3)
(4.4)

(4.5)
20

2 =

22 +2 +33
2

(4.6)

Here, MW signifies molecular weight, AW signifies atomic weight, and the subscript signifies
the species. TarC, TarH, TarO, TarN, and TarS come from Eqs (2.10) to (2.14) respectively.
Mass based coefficients are can be calculated as follows.
=

(4.7)

4.1.2
Chemical Rates
The chemical rate is based on the rate of flame combustion of C10H22 [3]. The assumption that tar
behaves as C10H22 is probably not accurate in all cases, but there is little information available to
build a comprehensive model.
30000

= 3.81011 exp

2 1.5 0.25

(4.8)

Here rTC is the reaction rate of tar combustion in mol/cm3, R is the universal gas constant in
cal/mol/K, Tg is the local gas temperature in K, g is the local gas volume fraction, g is the local
gas density, and X is the local weight fraction of the gas species in the gas phase.

4.2

Soot Oxidation

4.2.1
Mass Balance
The chemical reaction can be expressed as in Eq. (4.9). The coefficients are expressed in terms
of moles.
+ 252 252

(4.9)

4.2.2
Chemical Rates
The kinetics for soot oxidation in C3M are the same as those in PCCL which come from ShockTube Measurements of Soot Oxidation Rates by Park and Appleton [4, 5]. The rate expression
from Park and Appleton gives the soot oxidation rate in terms of flux of oxygen to a soot particle
surface in grams O2/cm2/s and is shown in Eqs. (4.10) to (4.12).

240 exp

15100
2

2060

1+21.3 exp

= 1 +

+ 5.35102 exp
1.51105 exp

4.46103 exp

2 =

2
2

48800

7640
2

7640

2 (1 )

(4.10)
(4.11)
(4.12)

Here, Tg is the local gas temperature in K, PO2 is the local partial pressure of oxygen in atm, g is
the local volume fraction of the gas, g is the local density of the gas in g/cm3, XO2 is the local
mass fraction of oxygen in the gas, MwO2 is the molecular weight of oxygen in g/mol and R is the
universal gas constant in cm3atm/K/mol.

21

The reaction for a single particle can then be expressed in terms of molar soot consumption with
the assumption that soot has a diameter of 0.8 m as is stated in Section 2.2.3. The rate in Eq.
(4.13) is in mol soot/s.

2
= 25

(4.13)

The number of particles per unit volume (cm3) can be calculated.

=

(4.14)

3
_

Thus, the overall rate for soot oxidation can be calculated in mol/cm3/s of soot consumption.

4.3

Char Oxidation

2
= = 25

(4.15)

2 _

Both MGAS and PCCL will give kinetics for char oxidation.
4.3.1
Mass Balance
In C3M, Char is assumed to be 100% carbon with a molecular weight of 12 g/mol. This yields a
mol based chemical reaction as shown in Eq. (4.16).
+ 2 2

(4.16)

4.3.2
Chemical Rate
The rate in MGAS is based on a shrinking core model with film diffusion, ash diffusion, and
reaction resistances. The rate in PCCL is based on a single nth order rate with an annealing
factor.
4.3.2.1
MGAS
The rate of production of CO is given in terms of mol/cm3/sec in Eq. (4.17).
=

The film resistance is given by:

6 2

(4.17)

1
1
1
+ + 2

(4.18)

The Sherwood number is calculated from Gunn [6].

1

= 7 10 + 52 1 + 0.7 0.2 3 + 1.33 2.4 + 1.22 0.7 3

The ash layer resistance is given by:

(1 )

The ratio of core diameter to particle diameter is given by:

(4.19)
(4.20)

22

= 0

The effective ash diffusivity is given by:

(4.21)

0
)
= 2 0.25 + 0.75(1

2.5

The diffusivity of oxygen is given by:

4.26

2 =

The surface reaction resistance is given by [7]:

(4.22)

1.75

1800

27000
2
1.987

= 8710 exp

(4.23)

In the above sets of equations, rCO is the rate of char oxidation in mol char/cm3/s, x is the local
volume fraction of phase x (g=gas, s=solid), x is the local density of phase x (g=gas, s=solid) in
g/cm3, PO2 is the local partial pressure of oxygen in atm, dp is the particle diameter in cm, kf is
the film resistance in gram oxygen/cm2/s/atm, ka is the ash layer resistance in gram
oxygen/cm2/s/atm, kr is the surface reaction resistance in gram oxygen/cm2/s/atm, DO2 is the
diffusivity of oxygen in cm2/s, Sh is the Sherwood number, dp is the particle diameter specified
by the user in cm, rp is the ratio of the core diameter to the outer diameter of the particle, R is the
universal gas constant in cm3atm/K/mol, MwO2 is the molecular weight of oxygen in g/mol, Tx is
the temperature of the phase x (g=gas, s=solid) in K, De is the effective diffusivity through the
ash layer in cm2/s, Xc and XAsh are the mass fractions of fixed carbon and ash respectively (the
superscript 0 means initial fuel content), and PTotal is the total pressure in atm.
4.3.2.2
PCCL
The advantage of this reaction chemistry form over MGAS is simplicity. Several computational
codes that are not open source (such as Barracuda) cannot implement such complex equation
forms as given by MGAS. While the MGAS kinetics are considered more accurate, it is
recommended that the PCCL kinetics be used when the CFD code will not allow the MGAS
form to be implemented.

PCCL reports the char oxidation kinetics in terms of mass consumption of oxygen flux across the
particle survace in g/cm2/s
=

6
2

exp

(4.24)

Here, CO is the annealing factor, ACO is the pre-exponential, EaCO is the activation energy, nCO is
the reaction order. These constants are retrieved and/or calculated from the
SNORC1CB1.RPT file from PCCL by C3M.
In the background, PCCL calculates the gasification kinetics of a char that does not experience
any annealing. It then compares those kinetics to the calculations of the CBKE model which
accounts for annealing and comes up with an annealing factor which is simply a polynomial
factor based on char conversion that acts as a rate multiplier to speed up or slow down the
gasification rate to account for annealing. PCCL actually supplies two equations, one for char

23

conversions less than 10% and one for char conversions over 10%. NETL has found that the
annealing factor reported by PCCL is not robust. PCCL most often fails to converge when
calculating this factor often resulting in an annealing factor of zero.
Therefore, NETL has developed a new method of calculating the annealing factor. PCCL does
report the CBKE data as a function of time which allows one to use an optimization routine to fit
a polynomial function of any order to the rate.
C3M allows the user to choose between these annealing factor methods on export. The PCCL
option is nothing more than the factors that PCCL reports. The Factor Fit option is the single
polynomial which has the order specified by the user. The Average is a zero order fit.
The carbon consumption for an individual particle can be calculated in mol char/s.
=

(4.25)

The number of particles per unit volume can be calculated.

= 3

Finally, the rate of consumption of char can be calculated in mol char/cm3/s.

4.4

CO Combustion

= =

6
2

(4.26)
(4.27)

The only sub-model that predicts CO combustion is MGAS.

4.4.1
Mass Balance
The mol based reaction is defined in Eq. (4.28).
1

+ 2 2 2

(4.28)

4.4.2
Chemical Rate
The rate used in MGAS comes from Westbrook and Dryer [3]. These kinetics are based on a
multistep model for the combustion of hydrocarbons.
40000

= 3.981014 exp

0.25

2
2

0.5

(4.29)

Here, R is the gas constant in cal/mol/K, Tg is the local gas temperature in K, g is the local
density of the gas in g/cm3, and Xa and Mwa are the mass fraction and molecular weight of
species a respectively. The rate (rCOComb) is expressed in terms of mol/cm3/s consumed.

4.5

H2 Combustion

The only sub-model which predict H2 combustion is MGAS.

4.5.1
Mass Balance
The mol based reaction is defined in Eq. (4.30).

24

2 + 2 2 2

(4.30)

4.5.2
Chemical Rate
The rate used in MGAS comes from Peters [8].

30000

2 = 1.081016 exp

2 2
2

(4.31)

Here, R is the gas constant in cal/mol/K, Tg is the local gas temperature in K, g is the local
density of the gas in g/cm3, and Xa and Mwa are the mass fraction and molecular weight of
species a respectively. The rate (rH2Comb) is expressed in terms of mol/cm3/s of hydrogen
consumption.

4.6

CH4 Combustion

The only sub-model which predicts CH4 combustion is MGAS.

4.6.1
Mass Balance
The mol based reaction is defined in Eq. (4.32).
4 + 22 2 + 22

(4.32)

4.6.2
Chemical Rate
The rate used in MGAS comes from Westbrook and Dryer [3].
48400

4 = 6.71012 exp

1.3

2
2

0.2

(4.33)

Here, R is the gas constant in cal/mol/K, Tg is the local gas temperature in K, g is the local
density of the gas in g/cm3, and Xa and Mwa are the mass fraction and molecular weight of
species a respectively. The rate (rCH4Comb) is expressed in terms of mol /cm3/s of methane
consumption.

4.7

Higher Hydrocarbon Combustion

The current version of C3M applies the same kinetics to higher hydrocarbon combustion as
methane. This is because the developers only recently began splitting higher hydrocarbons out
of the stoichiometry from methane and have not had the time to properly test and validate the
literature kinetics for all of the higher hydrocarbons produced in pyrolysis. This feature will be
coming in future versions of C3M.
4.7.1
Mass Balance
The general mass balance for hydrocarbon oxidation is expressed in terms of molar coefficients
in Eq. (4.34).

+ + 4 2 2 + 2 2

4.7.2
Chemical Rate
Until literature kinetics can be found, tested, and validated, the rate of higher hydrocarbon
combustion is the same as Eq. (4.33).

(4.34)

25

5. Water Gas Shift

The water gas shift reaction in C3M comes from MGAS [1, 9]. It is an ash catalyzed,
heterogeneous reaction which is significantly faster than the homogeneous reaction. This
reaction can only proceed in the presence of ash. If a shift catalyst is used or the homogeneous
reaction is used, the kinetics for water gas shift in C3M should not be used. These kinetics are
specific to water gas shift in a gasification environment.

5.1

Mass Balance

The water gas shift reaction is an equilibrium reaction and the mol based reaction is defined in
Eq. (5.1).

5.2

Chemical Rate

+ 2 2 + 2

(5.1)

The chemical rate for the reaction is expressed in mol/cm3/s.

5

= 2.87710 3 3

0.5 250

0
3 = 1

3 =

13978.71

8.91+5553

2 2
3

3.63061+3955.71

(5.2)

(5.3)
(5.4)

In these equations, PTotal is the total local pressure in atmospheres, Tg is the local gas temperature
in K, Xi is the local mass fraction of gas species i, s is the local solids density, g is the local
0
volume fraction of the gas, and
is mass fraction of ash in the proximate analysis.
The term wg3 represents the relative activity of the ash from coal and is supplied by C3M.

6. Methods for Estimating Thermodynamic Properties of Pseudo Species

There are several pseudo species within C3M. Pseudo species are species which represent a
collective of real chemical compounds for which it is either impossible or impractical to define a
list of chemical compounds and their fractional contribution to the whole of the pseudo species.
Therefore, one cannot define the thermodynamic properties based on a weighted sum of pure
chemical properties. At best, one can define the elemental composition, often by difference.
While this is not enough information to accurately pin down thermodynamic properties, it is
enough to make reasonable estimates. This section describes methods used to estimate heats of
formation and specific heats for pseudo species so that energy balances can be reasonably closed.
The methods descried here can be found in detail within Part 1 of the surrogate modeling series
(Van Essendelft et al., 2014).

6.1

Estimation of Heats of Formation for CHNOS Compounds

The heat of formation of the CHONS compounds can be estimated using a combination of the
Mason and Gandhi equation for estimating the heating value of the fuel and standard equations
for the heat of combustion. Translating the Mason and Gandhi equation to SI units, the dry ash
laden higher heating value for a fuel can be estimated as:

26


+ 18.82x106 + 10.46x106

= 46.08x106 + 144.28x106
11.98x106

(6.1)

, , and are the mass fractions of the elements and ash in the coal on a dry ash laden basis.
,
This will return the heat of combustion in J/kg. This equation is equation 5b) in Mason and
Ghandi converted to SI units.[10] Note also that Mason and Ghandis equation will produce a
positive value which means that their convention for exothermic reactions is opposite of what is
generally accepted, thus the negative sign in Eqn. (6.1).

To calculate the heat of formation we follow the method similar to that of Eisermann et al.[11]
Here we imagine an energy balance about a reactor where 1 kg of dry ash laden coal in an
isothermal reactor at the combustion temperature. Thus the energy needed to be removed to
maintain a constant temperature is exactly the heat of combustion. If it is assumed that all
carbon goes to CO2, all sulfur goes to SO2, all hydrogen goes to H2O, and all nitrogen goes to N2,
it is possible to define an energy balance that would yield the heat of formation of the CHONS
compound.

=
+ 2
+ 2
+ 2 2

(6.2)

Here, the pure component heats of formation have units of J/mol and the atomic weights
have units of kg/mol. This Eqn (6.2) is essentially Eqn 12 in Eisermanns paper but for a
batch system instead of a continuous flow system.[11]

6.2

Estimation of Specific Heat of CHONS compounds

For the solid CHONS compounds, the two characteristic temperature Einstein model proposed
by Merrick was implemented. The two-parameter Einstein model is succinctly summarized in
two equations.

380

1800

+ 2
exp()

() = ((exp()1))2

(6.6)

(6.7)

Here, the Cp is in J/g/K and the T is the temperature of the solid in K. This equation form is not
supported by most CFD codes which expect a fourth order polynomial. Thus the above equation
was fit using a least squares regression, split at a temperature of 1000K, and transformed into
units of Cp/R. The following table gives the coefficients that can be used to estimate the solid
CHONS compounds in Eq. (6.8).
T Range (K)
0-1000
1000-6000

A
9.297756e-12
-4.888334e-15

B
-2.331390e-08
8.025706e-11

C
1.848316e-05
-4.836515e-07

D
-2.659344e-03
1.285413e-03

E
7.397184e-01
1.669970e+00

27

= 4 + 3 + 2 + +

The above equation is applicable for coal, coal constituents, and coal-like compounds.

(6.8)

For ash, Merrick proposed using the following equation (after transformation):

= 8.57253933 + 8.45802261103

(6.9)

Standard relations used in petroleum processing were applied to estimate the specific heat of gas
phase CHONS compounds. Kesler and Lee report a correlation between molecular weight,
mean-average boiling point, and specific gravity.[12, 13]
= 12272.6 + 9486.4 + (8.3741 5.99175)
+(1 0.77084 0.02058 2 ) 0.7465

+(1 0.80882 0.02226 2 ) 0.3228

222.466 107

(6.10)

17.335 1012

Here, MW is the molecular weight of the hydrocarbon mixture in g/mol, SG is the specific
gravity, and Tb is the mean-average boiling point in units of Kelvin. Lee and Kesler also report
correlations for critical temperature and pressure based on specific gravity and mean-average
boiling point.
= 189.8 + 450.6 + (0.4244 + 0.1174) + (0.1441 1.0069)
ln( ) = 5.689

0.0566

0.43639 +

+ 0.47579 +

1.182

4.1216

0.15302 2

2
9.9099 3

2.4505 +

1010

106

0.21343
2

103

105

(6.11)
(6.12)

The Watson factor, Kw, can now be calculated for the hydrocarbon mixture. The Watson factor
is used to classify the type of hydrocarbons in the mixture based on the contents of paraffinic,
aromatic, and naphthenic compounds.
=

(1.8 )1/3

The acentric factor can now be estimated according to Lee and Kesler.

(6.13)

28

6.09648
6
+1.28862 ln( )0.169347

15.6875
6
15.2518
13.4721 ln( )+0.43577

ln( )5.92714+

(6.14)

Here Pbr is the reduced boiling point pressure (atmospheric pressure divided by the critical
pressure) and Tbr is the reduced boiling point temperature (Tb divided by the critical
temperature). This equation is good for reduced boiling temperatures of less than 0.8. For
reduced boiling temperatures higher than 0.8, Lee and Kesler suggest using the following
equation.
= 7.904 + 0.1352 0.0074652 + 8.359 +

(1.4080.01063 )

(6.15)

It is now possible to calculate the specific heat. Chang details the method used in Aspen Hysis
to calculate the specific heat from the Watson factor and the acentric factor.[14]
= [0 + 1 + 2 2 (0 + 1 + 2 2 )]

(6.16)

0 = 0.11828 1.41779

(6.17)

0 = 1.09223 2.48245

(6.20)

1 = (6.99724 8.69326 + 0.277152 )104

2 = 2.258210

1 = (3.434 7.14)103

2 = (7.2661 9.2561)107
=

(12.8 )(10 ) 2

10

(6.18)
(6.19)
(6.21)
(6.22)
(6.23)

Here, Cp is in J/g/K. The equation is generally valid up to about 1200C according to Chang.
However, Eq. (6.16) is an inverted parabola with a maximum between 1000K and 1200K. Most
substances do not decrease their specific heat with temperature because the degrees of freedom
available to the substance only increase with temperature. To approximate higher temperature
behavior, the value of the specific heat above 1000K was assumed to be that calculated by Eqs.
(6.16), (2.45) to (6.23) at 1000K.

7. Rate Limit Function

Many times, conditional statements can cause instabilities in a CFD code. In particular,
conditional statements that turn off rates when reagents are consumed can lead to small over
stepping past the point where reagents are consumed. Thus, C3M will often incorporate the "rate
limit" function as a multiplication factor in the rate expression. The function is as follows:

() = +

(7.1)
29

Here, x is the control variable (ie the concentration of the reagent) and y is a constant
which is a significantly small number. In the limit of x >> y, the function will return unity.
In the limit of x << y, the function will return zero. In the range of x ~= y, the function will
return a value between zero and 1 which decreases as x gets smaller. Thus the rate limit
function gently turns off the reaction without causing an instability. The user has the
ability to choose the value for y and thus the lower limit at which the rate is active.

8. Surrogate Modeling

Quite a bit of work has been done on surrogate modeling within C3M and has or is in the process
of being published in peer reviewed papers. The details of the derrivations and methods used
can be found in the paper series Advanced Chemistry Surrogate Model Development within
C3M for CFD Modeling. Part 1 is now public Futher parts will be forthcoming.[15]

References
1.
2.
3.

4.
5.
6.
7.

8.
9.

10.

11.
12.

Syamlal, M. and L.A. Bissett, METC Gasifier Advanced Simulation (MGAS) Model.
1992, National Technical Information Service: Springfield, Virginia.
ASTM International, Standard Practice for Proximate Analysis of Coal and Coke, in
ASTM Standard D3172-07a. 2007, ASTM International: West Conshohocken, Pa.
Westbrook, C.K. and F.L. Dryer, Simplified Reaction-Mechanisms for the Oxidation of
Hydrocarbon Fuels in Flames. Combustion Science and Technology, 1981. 27(1-2): p.
31-43.
Park, C. and J.P. Appleton, Shock-Tube Measurements of Soot Oxidation Rates.
Combustion and Flame, 1973. 20(3): p. 369-379.
Niksa, S., PC Coal Lab. 2008. Available from: http://www.niksaenergy.com/products/pccoal-lab/.
Gunn, D.J., Transfer of Heat or Mass to Particles in Fixed and Fluidized-Beds.
International Journal of Heat and Mass Transfer, 1978. 21(4): p. 467-476.
DeSai, P.R. and C.Y. Wen, Computer modeling of the Morgantown Energy Research
Center's fixed bed gasifier. 1978, United States Department of Energy: Morgantown,
WV.
Peters, N., Premixed Burning in Diffusion Flames - Flame Zone Model of Libby and
Economos. International Journal of Heat and Mass Transfer, 1979. 22(5): p. 691-703.
Wen, C.Y., H. Chen, and M. Onozaki, User's Manual for Computer Simulation and
Design of the Moving Bed Coal Gasifier. 1982, National Technical Information Service:
Springfield, Virginia.
Mason, D.M. and K. Gandhi, Formulas for Calculating the Heating Value of Coal and
Coal Char: Development, Tests and Uses, in ACS Fall Meeting. 1980, ACS: San
Francisco. p. 235-244.
Eisermann, W., P. Johnson, and W.L. Conger, Estimating Thermodynamic Properties of
Coal, Char, Tar and Ash. Fuel Processing Technology, 1980. 3(1): p. 39-53.
Kesler, M.G. and B.I. Lee, Improve Prediction of Enthalpy of Fractions. Hydrocarbon
Processing, 1976. 55(3): p. 153-158.
30

13.
14.
15.

Lee, B.I. and M.G. Kesler, A generalized thermodynamic correlation based on threeparameter corresponding states. Aiche Journal, 1975. 21(3): p. 510-527.
Chang, A.F., K. Pashikanti, and Y.A. Liu, Refinery Engineering: Integrated Process
Modeling and Optimization. 2013: Wiley.
Van Essendelft, D.T., T. Li, P. Nicoletti, and T. Jordan, Advanced Chemistry Surrogate
Model Development within C3M for CFD Modeling, Part 1: Methodology Development
for Coal Pyrolysis. Industrial & Engineering Chemistry Research, 2014. 53(18): p. 77807796.

31