Aspen Plus

Model for Entrained Flow Coal Gasifier

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Revision History
Version

Description

V7.2

First version

V7.3

Update the model to V7.3 and add a paragraph in Introduction section

to describe what files are released.

V7.3.2

Update the model to V7.3.2

V8.2

Update the model to V8.2

V8.4

Update the model to V8.4

Revision History

Contents
Revision History ......................................................................................................1
Contents..................................................................................................................2
Introduction ............................................................................................................3
1 Components .........................................................................................................4
2 Process Description..............................................................................................5
3 Physical Properties...............................................................................................7
4 Reactions .............................................................................................................9
4.1 Coal pyrolysis.............................................................................................9
4.1.1 Reactions......................................................................................9
4.1.2 Amount of each pyrolysis product ....................................................9
4.2 Volatile combustion................................................................................... 13
4.2.1 Reactions.................................................................................... 13
4.2.2 Reaction kinetics.......................................................................... 13
4.3 Char gasification....................................................................................... 14
4.3.1 Reactions.................................................................................... 14
4.3.2 Reaction kinetics.......................................................................... 15
5 Simulation Approach ..........................................................................................19
5.1 Unit Operations ........................................................................................ 20
5.1.1 Coal pyrolysis .............................................................................. 20
5.1.2 Volatile combustion ...................................................................... 20
5.1.3 Char gasification .......................................................................... 20
5.2 Streams .................................................................................................. 26
5.3 Calculator Blocks ...................................................................................... 26
5.4 Convergence ............................................................................................ 27
6 Simulation Results .............................................................................................28
7 Conclusions ........................................................................................................32
References ............................................................................................................33

Contents

Introduction

This file describes an Aspen Plus kinetics-based model for Texaco down-flow
entrained flow gasifiers. The model follows the modeling approach proposed
by Wen and Chaung[1].
The model includes the following features:

The model is a steady-state model.

The model accounts for major physical and chemical processes occurring
in the gasifier, i.e. coal pyrolysis, volatile combustion, and char
gasification.

The reaction kinetics for char gasification is considered.

The hydrodynamics to calculate solid residence time is taken into account.

The gas phase is assumed to be instantaneously and perfectly mixed with

the solid phase.

The pressure drop in the gasifier is neglected.

Coal particles are assumed to be spherical and of uniform size.

The ash layer formed remains on the particle during the reactions based
on the unreacted-core shrinking model[2].

The temperature inside the coal particle is assumed to be uniform.

The following files related to this example can be found in the

GUI\Examples\Entrained Flow Coal Gasifier folder of the Aspen Plus
installation:
Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.apwz, a compound
file containing these six files:

Introduction

Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.bkp

Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.pdf

USRKIN.f

USRPRES.f

USRSUB.dll

USRSUB.opt

Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.bkp

Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.pdf

USRSUB.dll

USRSUB.opt

1 Components

The following table represents the chemical species present in the process:

Table 1. Components Used in the Model

ID

Type

Name

Formula

O2

CONV

OXYGEN

O2

CO

CONV

CARBON-MONOXIDE

CO

H2

CONV

HYDROGEN

H2

CO2

CONV

CARBON-DIOXIDE

CO2

H2O

CONV

WATER

H2O

H2S

CONV

HYDROGEN-SULFIDE

H2S

N2

CONV

NITROGEN

N2

CH4

CONV

METHANE

CH4

C6H6*

CONV

BENZENE

C6H6

SOLID

CARBON-GRAPHITE

SOLID

SULFUR

COAL

NC

------

------

CHAR1*

NC

------

------

CHAR2*

NC

------

------

ASH

NC

------

------

*: C6H6 represents tar. CHAR1 represents the solid phase after coal pyrolysis
at 1atm. CHAR2 represents the solid phase after pressure correction from
1atm to system pressure.

1 Components

2 Process Description

The Texaco gasifier is a typical entrained flow gasifier, as shown in Fig. 1. The
total gasifier is divided internally into two sections[1, 3].

Figure 1. Schematic diagram of Texaco down-flow entrained flow gasifier[1]

The top section is for coal gasification. The pulverized coal with size typically
less than 500m[4] is mixed with water to form the coal-water slurry, and
then the slurry together with oxygen is simultaneously introduced into the top
section. Coal pyrolysis, volatile combustion and char gasification reactions
take place subsequently to produce the syngas. In this section, a special
refractory material is lined to withstand the severe operating environment.
The operating pressure is usually at 20-50atm and the temperature is
typically higher than 1000C[4].
The lower section is a quench vessel. A reservoir of water is maintained at the
bottom of the gasifier by continuous injection of cooling water. The slag and

2 Process Description

syngas leaving the top section of gasifier pass through a water-cooled dip
tube into the water reservoir. The slag remains in the water and then is
removed. The syngas is saturated with water and removed from the gas
space above the water.

2 Process Description

3 Physical Properties

In this model, the property method RK-SOAVE is used to calculate the

physical properties of mixed conventional components and CISOLID
components. HCOALGEN and DCOALIGT models are used to calculate the
enthalpy and density of non-conventional components, respectively.
The HCOALGEN model requires these three component attributes for nonconventional components: proximate analysis results (denoted as PROXANAL
in Aspen Plus), ultimate analysis results (denoted as ULTANAL in Aspen Plus),
and sulfur analysis results (denoted as SULFANAL in Aspen Plus). The
proximate analysis gives the weight contents of moisture, fixed carbon,
volatile matter, and ash. The ultimate analysis gives the weight composition
of coal in terms of ash, carbon, hydrogen, nitrogen, chlorine, sulfur, and
oxygen. The sulfur analysis gives the weight fractions of sulfur divided into
pyritic, sulfate, and organic sulfur. For the DCOALIGT model, it requires only
these two component attributes: ULTANAL and SULFANAL. Table 2 shows the
component attributes of coal used in our model, which are from the
literatures of Wen and Chuang[1, 5]. Based on these analysis results, the
enthalpy and density of coal are calculated, respectively.
For the characterization of char and ash generated in coal conversion, the
same methodology as the coal is applied and the same models are used to
calculate their enthalpy and density. The results of proximate, ultimate, and
sulfur analyses for the char and ash are determined from the analysis data of
original coal and the amount of gasified gaseous product in terms of mass
balance.

3 Physical Properties

[1,5]

Table 2. Component Attributes of Coal Used in the Model

Proximate analysis

Element
Moisture
(wet basis)
Fixed carbon
(dry basis)
Volatile matter
(dry basis)
Ash
(dry basis)

Ultimate analysis

Sulfur analysis

Value
(wt.%)

Element

Value
(wt.%, dry
basis)

Element

Value
(wt.%, dry
basis)

0.2

74.05

Pyritic

0.59

58.01

6.25

Sulfate

0.59

26.46

0.71

Organic

0.59

15.53

Cl

0.37

1.77

1.32

Ash

15.53

3 Physical Properties

4 Reactions

When the coal, oxygen and steam are simultaneously introduced into the
gasifier, these reactions take place in sequence: coal pyrolysis, volatile
combustion and char gasification.

4.1 Coal pyrolysis

4.1.1 Reactions
In gasifier, the temperature is typically higher than 1000C[4]. When coal is
fed into the gasifier, it first undergoes the pyrolysis process to decompose to
volatile matter and char, as shown in Eq. (1). In our model, volatile matter
includes CO, H2, H2O, CO2, CH4, H2S, N2 and C6H6. C6H6 is used to represent
the tar.

Coal Char CO H 2 H 2O CO2 CH 4 H 2 S N 2 C6 H 6

(1)

4.1.2 Amount of each pyrolysis product

In our model, the amount of each pyrolysis product is determined based on
the results of the pyrolysis experiment, which is made at 1atm. A pressure
correction is applied to the results of this experiment, adjusting them from
1atm to system pressure, to yield the amount of each product at the
operating conditions of the real gasifier. The next two sections describe how
to get the pyrolysis results at 1atm from the experiment and how to make a
pressure correction for the amount of each product.

4.1.2.1 Amount of each pyrolysis product at 1atm

Suuberg et al.[6] describe how to get the results of coal pyrolysis at 1atm in
experiment. Their corresponding results are summarized here. It should be
noted that in our model, the amount of each pyrolysis product at 1atm is from
the work of Wen and Chuang[1, 5].

4 Reactions

Flow chart of experiment

Fig. 2 is a schematic diagram for the apparatus of the pyrolysis experiment.
The apparatus consists of five components:

Reactor, which is designed to contain a coal sample in a gaseous

environment of known pressure and composition

Electrical system, which is used to expose the sample to a controlled timetemperature history

Time-temperature monitoring system

Product collection system

Product analysis system

A thin layer of coal particles with 74m average diameter are held in a folded
strip of stainless steel screen. Then, electricity is used to heat the coal
particles under 1atm helium or vacuum to produce the pyrolysis products.
After collecting the products, the yield of each product is analyzed.

Figure 2. The apparatus for the pyrolysis experiment in Suuberg et al.s

work[6]

Collection of pyrolysis products

The pyrolysis products can be divided into three types:

Products condensing at room temperature, such as tars

Products in the vapor phase at room temperature

Char

The first type of products is collected primarily on foil liners within the reactor
and on a paper filter at the exit of the reactor. Any condensation on non-lined
reactor surfaces is collected by washing with methylene-chloride-soaked filter
paper.
The second type of products is collected at the conclusion of a run by purging
the reactor vapors through two lipophilic traps. The first trap is operated at
room temperature with the Porapak Q chromatographic packing, and collects

10

4 Reactions

intermediate weight oils such as benzene, toluene and xylene. The second
trap is also packed with Porapak Q but operated at -196C in a dewar of liquid
nitrogen. This trap collects all fixed gases produced by pyrolysis, with the
exception of hydrogen which is determined by direct vapor phase sampling
with a precision syringe.
The third type of product, char, remains on the screen and is determined
gravimetrically.

Analysis of pyrolysis products

The different types of products collected are analyzed by different methods.
The first type of products is measured gravimetrically. The products of the
second type collected in the first and second traps are first warmed to 240C
and 100C, respectively, and then fed into the gas chromatography for
analysis. The third type of product is measured gravimetrically and its
elemental analysis is analyzed by the ASTM (American Society for Testing and
Materials) standard method. The analysis results are summarized in Fig. 3.

4.1.2.2 Amount of each pyrolysis product at

system pressure
Most pyrolysis experiments are carried out at 1atm. For example, all of
Suuberg et al.s results[6] shown in Fig. 3 are obtained at 1atm. However, in
real coal gasifiers, the pressure is usually much higher than 1atm, typically
20-50atm[4]. This indicates that the pressure effect on yield of each product
needs to be considered. In the pressure correction, the relative composition of
gas components is assumed to be constant, and only the total yield of
volatiles is corrected. The total yield of volatiles is corrected by Eq. (2)[1]:

V2 V1 1 a ln Pt

(2)

Where

V1 = total yield of volatiles at 1atm.

V2 = total yield of volatiles at the pressure of the real gasifier.
Pt = pressure in real gasifier, atm.
a = constant. In our model, a = 0.066.
Combining the total yield of volatiles calculated in Eq. (2) and the relative
composition of volatile products in the gas phase obtained from pyrolysis
experimental results at 1atm, the yield of each volatile product at the
operating conditions of real gasifier is calculated. Take the calculation of CO
yield as an example. Table 3 shows the yield of coal pyrolysis products at
1atm used in our model, which is from the work of Wen and Chaung[1, 5]. The
total yield of volatiles at 1atm is 27.28%, i.e. V1 27.28% . The relative

0.59% / 27.28% 2.16% . The gasifier in our

model is operated at 24atm, i.e. Pt 24atm . Based on Eq. (2),
V2 27.28% 1 0.066 ln 24 21.56% . Then, the yield of CO at system
pressure is 21.56% 2.16% 0.47% .
composition of CO in gas phase is

4 Reactions

11

(a)

(b)

(d)
(c)
[6]
Figure 3. Coal pyrolysis results of Suuberg et al.s work :
(a) Pyrolysis product distributions from lignite heated to different peak temperatures [()tar;
()tar and other hydrocarbons (HC); (*)tar, HC, and CO; ()tar, HC, CO, and CO2; (T)total, i.e.
tar, HC, CO, CO2, and H2O. Pressure=1atm (helium). Heating rate: (single points) 1000C/s;
(points inside ) 7100 to 10000C/s; (points inside ) 270 to 470C/s; (points inside )
1000C/s, but two-step heating;
(b) Yields of methane, ethylene, and hydrogen from lignite pyrolysis to different peak
temperatures [()CH4; (*)C2H4; ()H2. Pressure=1atm (helium); heating rate=1000C/s].
(c) Yields of water, carbon monoxide, and carbon dioxide from lignite pyrolysis to different peak
temperatures [()H2O; ()CO2; ()CO. Pressure=1atm (helium); heating rate=1000C/s].
(d) Elemental compositions of chars from lignite pyrolysis to different peak temperatures [(*)C;
()H; ()N; ()S; ()O. Pressure=1atm (helium); heating rate=1000C/s].

12

4 Reactions

After getting the yield of each volatile product, the yield of char is found by
subtracting the yield of all volatile products from unity.

Table 3. Yield of Coal Pyrolysis Products at 1atm Used in

the Model[1, 5]
Components

Yield (mass basis on original coal)

CO

0.0059

H2

0.0084

CO2

0.003

H2O

0.0079

H2S

0.0094

N2

0.0035

CH4

0.1637

C6H6

0.071

Char

0.7272

Total

4.2 Volatile combustion

4.2.1 Reactions
From Eq. (1), the volatile matter is composed of CO, H2, CO2, H2O, H2S, N2,
CH4, and C6H6. Among these gases, CO, H2, CH4, and C6H6 are combustible
gases. So after the coal pyrolysis, these combustible gases will react with
oxygen fed into the gasifier, as shown in reactions (3-6).

C 6 H 6 7.5O2 6CO2 3H 2O

(3)

H 2 0.5O2 H 2O

(4)

CO 0.5O2 CO2

(5)

CH 4 2O2 CO2 2 H 2O

(6)

4.2.2 Reaction kinetics

Since the reaction rate of gaseous combustion is generally fast and the
combustible gases will be consumed up in a short time, the reaction kinetics
of the volatile combustion process are neglected in the model. The
conversions of C6H6, H2, CO, and CH4 are assumed to be 100%.

4 Reactions

13

4.3 Char gasification

4.3.1 Reactions
After the volatile combustion process, the char from coal pyrolysis is further
gasified by the reaction with gases in the gas phase. This process may include
reactions (4-6) above, as well as reactions (7-13):

1
2
1
C O2 21 CO 1CO2

(7)

C H 2O CO H 2

(8)

C CO2 2CO

(9)

C 2 H 2 CH 4

(10)

S H 2 H 2S

(11)

CH 4 H 2O CO 3H 2

(12)

CO H 2 O CO2 H 2

(13)

In reaction (7),

is a coefficient which depends on the diameter of the coal

particle ( d p ) and can be calculated by the relations[1] in Table 4. Fig. 4 shows

the calculated relationship between
given temperature,

and d p at various temperatures. For a

is constant at d p 0.005cm and d p 0.1cm . At

0.005 d p 0.1cm , decreases with the increase in d p . For a given d p ,

shows a slight change with the temperature at d p 0.1cm . At d p 0.1cm ,

is independent of temperature and has the value of 1.0.

Table 4. Expressions of for Different Size of Coal

Particle[1]
dp

(cm)

<0.005

0.005-0.1

>0.1

Comment

2Z 2
Z 2

2 Z 2

Z d p 0.005

0.095
Z 2

CO
CO 2

2500 e

6249
T

1 .0

Note: CO and CO 2 are concentrations of CO and CO2, respectively. T is

temperature, K.

14

4 Reactions

Figure 4. Relationship between

and

at various temperatures

dp

4.3.2 Reaction kinetics

Reactions (7-11) are caused by the reaction of char with gaseous components
in the gas phase. The unreacted-core shrinking model[2] is used to describe
their kinetics. This is attributed to the following two points.

In the real gasifier, the char-gas reactions can be considered as surface

reactions because of high operating temperature (typically above
1000C).

Since the solid loading in the gasifier is usually very small, the particle
collision is infrequent and then the ash layer formed can be assumed to
remain on the particle during reactions.

In this model, the effects of ash layer diffusion, gas film diffusion and
chemical reaction are considered. The overall rate is expressed as Eq. (14):

RC i

1
1
k diff

1
1

2
k sY
k dash

P P

1
1
Y

(14)

Where

k diff = gas film diffusion constant, g/cm2atms.

4 Reactions

15

k s = surface reaction constant, g/cm2atms.

k dash = ash film diffusion constant, g/cm2atms. k dash k diff n , where is
voidage in the ash layer; n is a constant ranging from 2 to 3. In the model,
0.75 and n 2.5 .
1

r
1 x 3
, where rc is the radius of the unreacted core; rp is the
Y c
rp 1 f
radius of the whole particle including the ash layer; x is coal conversion at
any time after pyrolysis is completed, based on original d.m.m.f. coal; and f
is coal conversion when pyrolysis is completed, based on original d.m.m.f.
coal.

Pi Pi * = effective partial pressure of i-component taking account of the

reverse reaction, atm.

RC i = reaction rate, g of carbon/(cm2 of coal particle surface area)s.

The k diff ,

k s and Pi Pi * of reactions (7-10) from the work of Wen and

Chaung[1] are listed in Table 5. For the kinetics of reaction (11), we adopt the
expression similar to that of reaction (10), because the kinetics model is not
*
available now. The corresponding k diff , k s , and Pi Pi are given in Table 5.

In the derivation of Pi Pi

, the relationship between

K eq and T is found in

four steps:
1. Use a single RGibbs block to produce the equilibrium composition of
reaction (11) at various temperatures.
2. Calculate K eq at various temperatures based on the equation

K eq

PH 2 S
PH 2

, where PH 2 S and PH 2 are partial pressures, atm.

as Y-axis and 1/T as X-axis.

3. Make a linear fit with ln K eq

4. Transform the equation fitted in the third step to generate the

relationship between K eq and T.

16

4 Reactions

Table 5. Parameters for Kinetics of Reactions (7-11)

Reactions

k diff

(7)

4.26 T
0.292

T 1800
Pt d p

(8)

T
10 10 4

2000
Pt d p

(9)

T
7.45 10

2000
Pt d p

(10)

T
1.33 10

2000
Pt d p

(11)

T
1.33 10

2000
Pt d p

ks

Comment

Source

PO2

------

[1]

1.75

8710 e

17967
T

0.75

247 e

PH2 PCO

21060
T

PH2O

21060
T

PCO2

17921
T

PH2

PCH4

17921
T

PH 2

PH 2 S

K eq e

Keq

17 .644

30260
1 .8 T

[1]

0.75

247 e

------

[1]

0 .75

0.12 e

Keq

18400

K eq

0.175 1.8T

e
34173

[1]

0.75

Note: T=temperature, K;
particle, cm;

Pi Pi *

0.12e

K eq

K eq e

5.0657

18557 .7225
T

[1]*

Pt =total pressure, atm; d p =diameter of coal

is calculated according to the relations in Table 4. PO2 , PH 2O ,

PH 2 , PCO , PCO2 , PCH 4 and PH 2 S =partial pressures, atm. In the K eq expression

of reactions (8) and (10), the coefficient 1.8 before T is caused by the unit
conversion from Rankine degrees to Kelvin. [1]* means that the source is
from reference [1] and some changes are made for this model.
The kinetics of reactions (4-6) and (12-13) are shown in Table 6. The kinetics
of reaction (12) are modified according to the work of Wen and Chaung[1]. In
their work, the reaction rate of reaction (12) is described as 312e

30000
1.987T

CCH 4 ,

where the reaction rate of the reverse reaction is not considered. However,
the reaction of CH4 and H2O is generally reversible. So, the kinetics for the
CH4-H2O reaction are rewritten as the expression in Table 6. In deriving its
relationship between K eq and T, the steps are similar to those adopted for
reaction (11). The difference is that the calculation of K eq from the
equilibrium composition is based on the equation K eq

CCO C H3 2
CCH 4 C H 2O

, where

CCO , C H 2 , CCH 4 , and C H 2O are concentrations, mol/m3.

4 Reactions

17

Table 6. Kinetics of Reactions (4-6) and (12-13)

Reaction

Reaction rate

(4)

8 . 83 10 e

(5)

(6)

(12)

30 . 9 e

9 . 976 10 4
8 . 315 T

9 . 976 10 4
8 . 315 T

3 .552 10 e
11

312 e

30000
1 .987 T

C CO C O 2
9 .304 10 5
8 .315 T

C CH 4 C O2

C CO C H3 2
C CH
4

K eq C H 2O

Fw 2.77 10 xCO x
5

(13)

C H 2 CO2

Pt

P
0.5 t
250

*
CO

Comment

Unit

Source

------

mol/m3s

[7]

------

mol/m3s

[7]

------

mol/m3s

[7]

mol/m3s

[1]*

mol/[s(g
of ash)]

[1]

K eq e

PCO
Pt

*
x CO

1 PCO2 PH 2

Pt K eq PH 2O

K eq e
Note: T=temperature, K; C H 2 , C O2 ,
mol/m3;
atm;

25014 .0499
T

xCO
27760
1.987 T

5553
8.91
T

33 .1371

3 .6893

7234
1 .8 T

CCO , CCH 4 , and C H 2O =concentrations,

PCO , PCO2 , PH 2 , and PH 2O =partial pressures, atm; Pt =total pressure,

Fw =adjustable parameter, which represents the relative catalytic

reactivity of ash to that of iron-base catalyst. In the model, Fw 0 .2 . In the

reaction rate expressions of reactions (4-6), the coefficient 8.315 before T
stands for the universal gas constant in J/molK. In reaction rate expressions
of reactions (12-13), the coefficient 1.987 before T means the universal gas
constant in cal/molK. In the

K eq

expression of reaction (13), the coefficient

1.8 before T is caused by the unit conversion from Rankine degrees to Kelvin.
[1]* means that the source is from reference (1) and some changes are made
for this model.

18

4 Reactions

5 Simulation Approach

Fig. 5 shows the flowsheet for the whole coal gasification process. The quench
section for cooling the hot gas from the gasification section is not simulated in
this model. The function of each block is shown in Table 7. PYROLYS and
PRESCORR blocks are used to simulate the coal pyrolysis process. The
COMBUST block is used to model the volatile combustion process. The
GASIFIER block is for the char gasification process. Other blocks are used for
helping these four blocks to simulate the above three processes.

Figure 5. Flowsheet for coal gasification

5 Simulation Approach

19

Table 7. Function of Each Block

Block

Model

Function

PYROLYS

RYield

Simulate the coal pyrolysis based on the results of the

pyrolysis experiment at 1atm

PRESCORR

RYield

Make pressure correction for the yield of each product from

the pressure in the pyrolysis experiment (i.e. 1atm) to the
pressure in the real gasifier

SEPSG

Sep2

Separate the gas and solid char

COMBUST

RStoic

Model the volatile combustion

SEPELEM

RStoic

Decompose char into C, H2, O2, N2, S, and ash in order to

easily deal with the solid reactions in GASIFIER block

MIXER

Mixer

Mix the feedstock for the GASIFIER block

GASIFIER

RPlug

Model the char gasification process

SPELMCAL

Calculator

Determine the stoichiometric coefficients of C, H2, O2, N2, S,

and ash in reaction of the SEPELEM block

GASIFCAL

Calculator

Correct the solid residence time in the GASIFIER block

5.1 Unit Operations

5.1.1 Coal pyrolysis
In the model, coal pyrolysis process is simulated with two RYield reactors, the
PYROLYS and PRESCORR blocks. The first RYield reactor, PYROLYS, is used to
simulate the coal pyrolysis at 1atm based on the results of the pyrolysis
experiment. The second RYield reactor, PRESCORR, is used to make a
pressure correction for the yield of each component generated in the
PYROLYS block. The correction method is described in section 4.1.2.2. In the
model, the correction is automatically done by a user-subroutine called
USRPRES.

5.1.2 Volatile combustion

Since the reaction rate of volatile combustion is generally fast and the
combustible gases can be considered to be consumed up in a short time, the
kinetics of volatile combustion process is neglected in the model. An RStoic
reactor, the COMBUST block, is used to simulate the volatile combustion
process. The fractional conversions of combustible gases are all set as 1.0.

5.1.3 Char gasification

In the model, the char gasification process is model with an RPlug reactor, the
GASIFIER block. In this process, the reaction kinetics and residence time of

20

5 Simulation Approach

char are the two main factors affecting the remaining carbon conversion and
product composition.

5.1.3.1 Treatment of reaction kinetics

From the kinetics models in section 4.3.2, most kinetics are so complex that
they cant be treated by the built-in kinetics expression template in Aspen
Plus. So these reactions' kinetics are provided in a user subroutine called
USRKIN. In the user kinetics subroutine of RPlug, the output is the reaction
rate of each component taking part in the reactions. The reaction rate of each
conventional component must be provided in the unit of kgmole/ms. This
unit is derived by the relation that rates per unit volume are multiplied by the
cross-sectional area covered by the reacting phase, i.e. kgmole/ms =
(kgmole/m3s)(m2). So in order to get the required reaction rate of each
component, the following two steps are taken.
1. Convert the unit of each reaction rate in section 4.3.2 to kgmole/ms.
2. Calculate the total reaction rate of each component according to the
stoichiometry of reactions.

Unit conversion for rate of each reaction

The rates of reactions (7-10) are in the unit of g of carbon/(cm2 of coal
particle surface area)s. The conversion of this unit follows the steps shown in
Fig. 6. In the conversion, the coal particle is assumed to be spherical.

Figure 6. Schematic diagram for unit conversion of reactions (7-10)

1
C i

4rp2
RC i
4 3
r p
3

Step 1:

Step 2:

RC2 i RC1 i

10 3 / 12
10 6

Step 3:

RC3 i RC2 i

2
D 1 Vbed
4

Combining above three steps gives the following total conversion expression:

5 Simulation Approach

21

RC3 i RC i

D 2
1 Vbed
16 10 3 rp

(15)

Where

rp

= radius of coal particle, cm.

D = diameter of gasifier, m.

Vbed

= void fraction in gasifier.

fraction in gasifier.

V particle

Vbed 1 V particle , where V particle

Fcoal t coal
4 D 2 h

is residence time of coal in the gasifier;

gasifier length.

Vbed

, where

coal

Fcoal

is particle

is coal flow rate;

is coal density; and

is

is first calculated in a calculator block called GASIFCAL,

then transferred back to the user kinetics subroutine.

The unit of reaction (11)s rate ( R S H 2 ) is g of sulfur/(cm2 of coal particle
surface area)s, which is very similar to the unit of reactions (7-10). The
difference is that we just change the molecular weight of carbon to that of
sulfur. The final relation is:

R S3 H 2 RS H 2

3D 2
1 Vbed
128 10 3 rp

(16)

The units for rates of the four gaseous reactions (4-6) and (12) are
mol/m3(gas phase)s. The steps for this unit conversion are shown in Fig. 7.

Figure 7. Schematic diagram for unit conversion of reactions (4-6) and (12)

Step 1:

Ri1 Ri 10 3

Step 2:

Ri2 Ri1

2
D Vbed
4

Based on the above two steps, the total conversion expression is:

Ri2 Ri 10 3

D 2
Vbed
4

(17)

For reaction (13), the rate of reaction ( RCO H 2O ) is in the unit of mol/[s(g of
ash)]. The unit conversion takes the steps shown in Fig. 8.

22

5 Simulation Approach

Figure 8. Schematic diagram for unit conversion of reaction (13)

Step 1:

1
RCO
H 2O RCO H 2O 1 Ymoisture Yash

Step 2:

2
1
RCO
H 2O RCO H 2 O coal

Step 3:

3
2
RCO
H 2 O RCO H 2O

10 3
10 6

Step 4:

4
3
RCO
H 2 O RCO H 2O

2
D 1 Vbed
4

Combining above four steps yields the total conversion expression:

4
RCO
H 2 O RCO H 2 O 1 Ymoisture Yash coal

D 2
1 Vbed
4 10 3

(18)

Where

Ymoisture
Yash

= moisture fraction in original coal, wet basis.

= ash fraction in original coal, dry basis.

Total reaction rate of components

After making the unit conversion for the rate of each reaction, we can get the
total reaction rate of each component according to the stoichiometry of
reactions. Take the total reaction rate of H2 as an example. From sections
4.2.1 and 4.3.1, there are six reactions involving H2, which are reactions (4),
(8), and (10-13). The stoichiometric coefficient of H2 in each reaction is listed
in Table 8. Meanwhile, the abbreviation for the rate of each reaction is also
listed in Table 8. Based on Table 8, the total reaction rate of H2 is:
2
4
R H 2 RC3 H 2O RC3 H 2 2 RS3 H 2 RH2 2 O2 RCH
3 RCO
H 2O
4 H 2O

5 Simulation Approach

(19)

23

Table 8. Stoichiometric Coefficient of H2 in Each Reaction

and Abbreviation of Each Reaction Rate
Reactions

Stoichiometric
coefficient of H2

Rate of reaction
(kgmole/ms)

(4)

-1

R H2 2 O2

(8)

RC3 H 2O

(10)

-2

RC3 H 2

(11)

-1

R S3 H 2

(12)

2
RCH
4 H 2O

(13)

4
RCO
H 2O

Note: If H2 is a reactant, the coefficient is negative. If H2 is a product, the

coefficient is positive.

5.1.3.2 Residence time of solid

In the model, the char gasification process is simulated by an RPlug reactor.
In RPlug, the residence time is calculated by Eq. (20):
VR

1
dVR
V

(20)

Where

VR

= reactor volume.
= volumetric flow rate of gases.

In Eq. (20), V is the product of gas velocity multiplied by cross-sectional

area of the reactor. This means that the calculation of residence time in RPlug
mainly depends on the velocity of the gas phase. However, the solid
residence time is closely related to the velocity of the solid phase. So to get
the correct residence time of solids in the GASIFIER block, an external Fortran
Calculator block called GASIFCAL block is used to calculate the solid residence
time before executing the GASIFER block. This Calculator block includes three
main parts:
1. Selection of model of downward velocity of solid;
2. Calculation of solid residence time;
3. Return of results from the GASIFCAL block to the GASIFIER block.

Selection of model of downward velocity of solid

In the entrained-flow gasifier, the coal particle size is very small, typically less
than 500m[4]. Using the coal parameter of 500m and the input conditions in

24

5 Simulation Approach

Tables 2-3 and 11-12, the viscosity (), velocity (u) and density () of
product gases at the outlet of gasifier are calculated by this Aspen Plus
model. = 5.7310-5Pas. u = 0.03m/s. = 3.03kg/m3. Then, the Reynolds
number of particles is calculated to be 0.79 based on the equation

Re p

d p u

, where d p is the coal particle diameter, 510-4m. In the whole

gasifier, the temperature at the outlet is the lowest, indicating the and of
gases at the outlet are the lowest and the largest, respectively. Meanwhile,
the amount of product gases is the largest at the outlet of the gasifier, and
then the corresponding u of gases is the largest in the whole gasifier. So, we
can assume that the Re p in the whole gasifier is less than 0.79. Considering
the valid regime of Stokes law, i.e. Re p 2 [8], we can conclude that Stokes
law is applicable for the solid flow in this system. According to Newtons
second law and Stokes law, Eq. (21) is derived for downward velocity of solid
( vs )[1].

vs vs ,i e bt v g vt 1 e bt

(21)

Where

18
.
s d p2

vt = terminal settling velocity of particle in a static fluid. vt

where v s ,i

g d p2 g

18
is initial velocity of solid; v g is velocity of gas phase; is gas

viscosity; s is density of solid; g is density of gas; d p is diameter of solid

particles.

Calculation of solid residence time

Integrating Eq. (21) gives the relationship between gasifier length (h) and
solid residence time (t):

vs ,i
1 e bt
bt
h vs dt
1 e v g vt t
0
b
b

(22)

Based on Eq. (22), the solid residence time is calculated by Newtons method.
In the calculation, g , , and v g use the values at the inlet of the GASIFIER
block; s takes the average value in the gasifier based on the harmonious
square root, i.e. s

2 s2,i s2,o

s2,i s2,o

, where s ,i and s,o are the solid densities

at the inlet and outlet of GASIFIER block, respectively. Because the

conversion of useful components in coal is generally close to 100% in
practical application, we assume that the solid density at the outlet of the
gasifier is equal to the density of ash, i.e. s ,o coal 1 Ymoisture Yash , where

5 Simulation Approach

25

 coal is inlet coal density; Ymoisture is moisture content in coal, wet basis; and
Yash is ash content in coal, dry basis.

Return of results from GASIFCAL to GASIFIER

Through the above calculation, the solid residence time in the gasifier has
been approximately calculated in the GASIFCAL block. The next step is to
transfer the results from the GASIFCAL block to the GASIFIER block, so that
the solid residence time in the GASIFIER block can be corrected
correspondingly. However, in the GASIFIER block, the residence time is used
as an output variable, not an input variable. This means that the solid
residence time cannot be transferred directly, so another route is taken. The
diameter of the gasifier, which is an input variable in the GASIFIER block, is
used as the transferred variable.
The residence time calculated in GASIFCAL block is first transformed to the
gasifier diameter (D) based on Eq. (23):

Vg t

2
D h
4

(23)
Where

Vg

= volumetric flow rate of gas phase at the inlet of GASIFIER block.

= residence time.

= gasifier length.

Transforming Eq. (23) gives the expression for D:

Vg t

h
4

(24)

After getting the gasifier diameter based on Eq. (24) and transferring it to the
GASIFIER block, the solid residence time in the GASIFIER block is corrected
correspondingly.

5.2 Streams
Streams represent the material and energy flows in and out of the process.
This model includes two types of streams, material and heat streams, as
shown in Fig. 5. The streams with solid lines represent material streams. The
streams with dashed lines represent heat streams.

5.3 Calculator Blocks

This model includes two Calculator blocks, as shown in Table 9.

26

5 Simulation Approach

Table 9. Calculators Used in the Model

Name

Function

SPELMCAL

Determine the stoichiometric coefficients of C, H2, O2, N2, S, and ash

in reaction of the SEPELEM block

GASIFCAL

Correct the solid residence time in the GASIFIER block

5.4 Convergence
The convergence method impacts simulation performance greatly.
Inappropriate convergence methods may result in the failure of convergence
or long running time. In this model, the choice of convergence method for the
RPlug reactor called GASIFIER is very important. The convergence parameters
for the GASIFIER block in the example model are summarized in Table 10.
These are specified on the sheet Blocks | GASIFIER | Convergence |
Integration Loop.

Table 10. Convergence Parameters for GASIFIER Block

Items

Integration
parameters

Corrector
Integration error

5 Simulation Approach

Parameters

Setup

Integration convergence tolerance

0.0001

Initial step size of integration variable

1E-8

Maximum step size of integration variable

0.001

Maximum number of integration steps

1E6

Convergence method

Newton

Error tolerance ratio

0.1

Error scaling method

Dynamic

Minimum scale factor

1E-10

27

6 Simulation Results

In this model, the input conditions for the simulation and the corresponding
experimental results are from the open literature[1, 5]. The input conditions for
the simulation are summarized in Tables 2, 3, 11, and 12. Table 2 gives the
component attributes of coal including the results of proximate, ultimate, and
sulfur analyses. Table 3 shows the yield of each pyrolysis product obtained
from the coal pyrolysis experiment at 1atm. Table 11 summarizes the feed
conditions of coal, steam, and oxygen streams. For the coal stream, it
includes the flow rate of coal, inlet temperature and pressure, diameter of
coal particle, and velocity of coal particle entering into the gasifier. For the
steam stream, it contains the ratio of steam to coal flow rates, inlet
temperature, and pressure. At our feed conditions of 696.67K and 24atm, the
steam enters the gasifier in a superheated state. For the oxygen stream, it
includes the ratio of oxygen to coal flow rates, inlet temperature, and
pressure.

Table 11. Feedstock Conditions for Simulation[1, 5]

Feedstock

Coal

Oxygen

Steam

Parameter

Value

Unit

Flow rate

76.66

g/s

Temperature

505.22

Pressure

24

atm

Diameter of particle

350

Velocity entering into gasifier

m/s

Ratio of oxygen to coal flow rates

0.866

dimensionless

Temperature

298

Pressure

24

atm

Ratio of steam to coal flow rates

0.241

dimensionless

Temperature

696.67

Pressure

24

atm

Table 12 gives the operating conditions and configuration parameters of the

gasifier, which are the operating pressure, gasifier length, and diameter. In
the work of Wen and Chaung[5], they assume that the coal pyrolysis and
volatile combustion processes account for 4.6% of the length of whole
gasifier. So in our model, the length for char gasification process simulated in
the GASIFIER block is set as 325 (1 4.6%) 310cm .

28

6 Simulation Results

Table 12. Operating Condition and Configuration of

Gasifier[1, 5]
Parameter

Value

Unit

Pressure

24

atm

Length

3.25

Diameter

1.5

Based on above input conditions, we get the results at the outlet of the
gasifier, as shown in Table 13 as Aspen Plus model a. For comparison, the
corresponding results of Wen and Chaungs work[1] are also shown in the
table. From the table, it can be seen that Wen and Chaungs results[1] are in a
better agreement with experimental data. In our simulation results, the CO
and CO2 flow rates and carbon conversion are somewhat different from the
experimental data. The CO flow rate and carbon conversion are greater than
the experimental data. The CO2 flow rate is less than the experimental data.
The difference in CO and CO2 flow rates and carbon conversion may be
attributed to the higher temperature in the gasifier calculated by our model.
In our model, the temperature at the outlet of gasifier is 1771.2K. However,
the outlet temperature is 1421.9K in Wen and Chaungs model. The increase
in temperature of gasifier speeds up the reaction rate of solid carbon and
gases, i.e. rate of reactions (7-10), and then makes the carbon conversion in
our simulation greater than the experimental data. The difference in flow
rates of CO and CO2 depends on reaction (13), an exothermic reaction.
Increasing the temperature will make the reaction shift in the backward
direction, i.e. increasing the amount of CO and decreasing the amount of CO2.
So, increasing the temperature decreases the simulated CO2 flow rate and
increases the simulated CO flow rate.
Why does our simulation generate the higher temperature in the gasifier? This
may be caused by two points. The first point is the heat of combustion
(HCOMB) of coal. In our model, the HCOMB of coal is calculated by the builtin method (Boie correlation) in Aspen Plus due to lack of accurate
experimental data. However, we believe the HCOMB has a significant effect
on the enthalpy of coal. So, the inaccurate HCOMB may make the incorrect
enthalpy of coal and then result in the large departure of gasifier
temperature. The second point is the amount of heat loss in the gasifier. In
our work, the model is simulated in an adiabatic mode. In Wen and Chaungs
model[1], the heat loss to the environment is considered. Therefore,
combining these two points may cause the higher temperature of the gasifier
in our model.
In order to further validate our explanation that the difference in CO and CO2
flow rates and carbon conversion is caused by the higher temperature in our
model, we manually input the HCOMB of coal to match our outlet temperature
with Wen and Chaungs work.

6 Simulation Results

29

Table 13. Comparison of Experimental and Modeling

Results
Experimental[1]
Parameters

Flow
rate
(g/s)

Mole
fraction
(%, dry
basis)

Wen and
Chaungs
model[1]
Flow
rate
(g/s)

Mole
fraction
(%, dry
basis)

Aspen Plus
model a
Flow
rate
(g/s)

Mole
fraction
(%, dry
basis)

Aspen Plus
model b
Flow
rate
(g/s)

Mole
fraction
(%, dry
basis)

CO

123.77

57.57

123.94

56.60

127.71

58.98

123.44

57.41

H2

6.01

39.13

6.23

39.84

5.96

38.23

5.99

38.71

CO2

9.985

2.95

10.04

2.92

6.462

1.90

10.24

3.03

CH4

0.15

0.12

0.20

0.16

0.13

0.10

0.24

0.20

H2S

0.133

0.06

0.726

0.27

1.405

0.53

1.04

0.40

N2

0.53

0.12

0.454

0.208

0.54

0.25

0.54

0.25

Carbon conv. (%)

98.64

98.88

99.95

98.69

Temp. (K)

------

1421.9

1771.2

1423.2

Note: In model a, HCOMB of coal is calculated by Boie correlation; in model

b, HCOMB of coal is manually input as 13416Btu/lb.
When the HCOMB of coal is input as 13416Btu/lb (compared with the HCOMB
of coal calculated as 14080.83Btu/lb by the Boie correlation), the outlet
temperature is equal to 1423.2K, which matches the temperature (1421.9K)
in Wen and Chaungs work. At the same time, the CO and CO2 flow rates and
carbon conversion are also in a good agreement with the experimental data,
as shown in Table 13 as Aspen Plus model b. Fig. 9 shows the corresponding
profile of main product gases (CO, H2, H2O, and CO2) in char gasification
process. In Fig. 9b, Wen and Chaung show the profile of product gas in the
whole gasifier and the corresponding profile in the char gasification process is
marked on the figure. Our model shows a similar result to Wen and Chaungs
model. As the residence time increases, H2O and CO2 contents in the gas
phase decrease, and CO and H2 contents increase.
Based on these phenomena, it can be determined that the product gas
composition and carbon conversion are strongly dependent on the
temperature in the gasifier, and HCOMB of coal and heat loss are two key
parameters in determining the temperature in the gasifier.

30

6 Simulation Results

VOL. %(Wet basis)

70

70

60

60

50

50

40

40

30

30
CO
H2

20

20
H2O
CO2

10

10

0
0

10

Residence time (s)

(a)

(b)
Figure 9. Profile of product gas composition: (a) in char gasification process
based on Aspen Plus model and (b) in whole gasifier based on Wen and
Chaungs model[1] (solid residence time in whole gasifier is 9.5s).

6 Simulation Results

31

7 Conclusions

A Texaco down-flow entrained flow gasifier model is developed with the Aspen
Plus simulator. The model follows the modeling approach suggested by Wen
and Chaung[1]. In the model, the kinetics of char gasification and the
hydrodynamics for calculating solid particle residence time are considered.
Reasonable simulation results were obtained compared with the experimental
results. The Aspen Plus model provides a useful modeling framework for
future refinements as new knowledge is gained with the entrained flow
gasifier. To use this model, the following data should be provided:

Component attributes and higher heat of combustion of coal. The

component attributes of coal include the data of proximate, ultimate, and
sulfur analyses.

Yield of coal pyrolysis products from coal pyrolysis experiment at

1atm.

Feed conditions of coal, oxygen and steam streams, which include

the flow rate, temperature and pressure. The coal stream also includes
the diameter of coal particle and velocity fed into the gasifier.

Configuration parameters and operational conditions of the

gasifier, which include gasifier height, gasifier diameter, operating
pressure, and heat loss. The heat loss can also be in-situ calculated by
providing heat transfer coefficient and environmental temperature.

Model parameters, which include porosity of ash layer and reactivity of

ash for the reaction of CO and H2O.

From the model, the following information can be obtained:

32

Profile of flow rate of products

Profile of carbon conversion

Profile of temperature

Pressure of exit gas and solid

Solid residence time in the gasifier

7 Conclusions

References

References

[1]

C.-Y. Wen, T.-Z. Chaung, Entrainment coal gasification modeling, Ind.

Eng. Chem. Process Des. Dev., 18: 684-695, 1979.

[2]

C.-Y. Wen, Noncatalytic heterogeneous solid fluid reaction models,

Ind. Eng. Chem., 60: 34-54, 1968.

[3]

R. Govind, J. Shan, Modeling and simulation of an entrained flow coal

gasifier, AIChE J., 30: 79-92, 1984.

[4]

S.-S. Xu (), D.-L. Zhang (), Y.-Q. Ren (), Large-scale

coal gasification technology (), Beijing: Chemical
Industry Press, 2006.

[5]

C.-Y. Wen, T.-Z. Chaung, Entrained-bed coal gasification modeling,

Report submitted to Department of energy, Contract E(49-18)274,
1978.

[6]

E.M. Suuberg, W.A. Peters, J.B. Howard, Product composition and

kinetics of lignite pyrolysis, Ind. Eng. Chem. Process Des. Dev., 17:
37-46, 1978.

[7]

K.-F. Cen (), M.-J. Ni (), Z.-Y. Luo (), J.-H. Yan (
), Y. Chi (), M.-X. Fang (), X.-T. Li (), L.-M. Cheng (
), Theory, design and operation of circulating fluidized bed boilers (
), Beijing: Chinese Electric Power Press,
1998.

[8]

H. Masuda, K. Higashitani, H. Yoshida, Powder technology handbook

(3rd edition), CRC Press, 2006.

33