Documente Academic
Documente Profesional
Documente Cultură
Revision History
Version
Description
V7.2
First version
V7.3
V7.3.2
V8.2
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 accounts for major physical and chemical processes occurring
in the gasifier, i.e. coal pyrolysis, volatile combustion, and char
gasification.
The ash layer formed remains on the particle during the reactions based
on the unreacted-core shrinking model[2].
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:
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].
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
3 Physical Properties
[1,5]
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 Reactions
Electrical system, which is used to expose the sample to a controlled timetemperature history
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.
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.
V2 V1 1 a ln Pt
(2)
Where
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.
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
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 Reactions
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),
(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
14
4 Reactions
and
at various temperatures
dp
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
4 Reactions
15
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.
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
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
16
4 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]*
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
17
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
K eq
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.
5 Simulation Approach
19
Model
Function
PYROLYS
RYield
PRESCORR
RYield
SEPSG
Sep2
COMBUST
RStoic
SEPELEM
RStoic
MIXER
Mixer
GASIFIER
RPlug
SPELMCAL
Calculator
GASIFCAL
Calculator
20
5 Simulation Approach
char are the two main factors affecting the remaining carbon conversion and
product composition.
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
D = diameter of gasifier, m.
Vbed
fraction in gasifier.
V particle
Fcoal t coal
4 D 2 h
Vbed
, where
coal
Fcoal
is particle
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
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
D 2
1 Vbed
4 10 3
(18)
Where
Ymoisture
Yash
5 Simulation Approach
(19)
23
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
1
dVR
V
(20)
Where
VR
= reactor volume.
= volumetric flow rate of gases.
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
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
g d p2 g
18
is initial velocity of solid; v g is velocity of gas phase; is gas
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
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.
Vg t
2
D h
4
(23)
Where
Vg
= residence time.
= gasifier length.
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.
26
5 Simulation Approach
Function
SPELMCAL
GASIFCAL
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.
Integration
parameters
Corrector
Integration error
5 Simulation Approach
Parameters
Setup
0.0001
1E-8
0.001
1E6
Convergence method
Newton
0.1
Dynamic
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.
Coal
Oxygen
Steam
Parameter
Value
Unit
Flow rate
76.66
g/s
Temperature
505.22
Pressure
24
atm
Diameter of particle
350
m/s
0.866
dimensionless
Temperature
298
Pressure
24
atm
0.241
dimensionless
Temperature
696.67
Pressure
24
atm
28
6 Simulation Results
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
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
98.64
98.88
99.95
98.69
Temp. (K)
------
1421.9
1771.2
1423.2
30
6 Simulation Results
70
70
60
60
50
50
40
40
30
30
CO
H2
20
20
H2O
CO2
10
10
0
0
10
(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:
32
Profile of temperature
7 Conclusions
References
References
[1]
[2]
[3]
[4]
[5]
[6]
[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]
33