Professional Documents
Culture Documents
Aspen Plus, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered
trademarks of Aspen Technology, Inc., Burlington, MA.
All other brand and product names are trademarks or registered trademarks of their respective companies.
This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1
This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech
proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of
AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of
the software and the application of the results obtained.
Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software
may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO
WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION,
ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE.
Revision History 1
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
7 Conclusions ........................................................................................................32
References ............................................................................................................33
2 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:
o Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.bkp
o Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.pdf
o USRKIN.f
o USRPRES.f
o USRSUB.dll
o USRSUB.opt
Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.bkp
Aspen_Plus_Model_for_Entrained_Flow_Coal_Gasifier.pdf
USRSUB.dll
USRSUB.opt
Introduction 3
1 Components
The following table represents the chemical species present in the process:
*: 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.
4 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].
2 Process Description 5
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.
6 2 Process Description
3 Physical Properties
3 Physical Properties 7
[1,5]
Table 2. Component Attributes of Coal Used in the Model
Proximate analysis Ultimate analysis Sulfur analysis
Value Value
Value
Element Element (wt.%, dry Element (wt.%, dry
(wt.%)
basis) basis)
Moisture
0.2 C 74.05 Pyritic 0.59
(wet basis)
Fixed carbon
58.01 H 6.25 Sulfate 0.59
(dry basis)
Volatile matter
26.46 N 0.71 Organic 0.59
(dry basis)
Ash
15.53 Cl 0.37
(dry basis)
S 1.77
O 1.32
Ash 15.53
8 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 9
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 time-
temperature 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.
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)
(c) (d)
[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.
H 2 0.5O2 H 2O (4)
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 1 2
C O2 21 CO 1CO2 (7)
C H 2O CO H 2 (8)
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)
2Z 2
<0.005
Z 2
Z d p 0.005 Z
CO
0.005-0.1
2 Z 2 CO 2
0.095
Z 2
6249
2500 e T
>0.1 1 .0
14 4 Reactions
Figure 4. Relationship between and dp at various temperatures
RC i
1 1
1
1 1
P P
i i
*
(14)
1
Y
2
k diff k sY k dash
Where
k diff = gas film diffusion constant, g/cm2atms.
4 Reactions 15
k s = surface reaction constant, g/cm2atms.
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.
16 4 Reactions
Table 5. Parameters for Kinetics of Reactions (7-11)
Reactions k diff ks Pi Pi * Comment Source
1.75
4.26 T
0.292
17967
(7) T 1800 8710 e T PO2 ------ [1]
Pt d p
0.75
T
10 10 4 PH2 PCO 30260
PH2O 17 .644
21060
(8) 2000 247 e T
Keq K eq e 1 .8 T [1]
Pt d p
0.75
4 T
7.45 10
21060
(9) 2000 T PCO2 ------ [1]
247 e
Pt d p
0 .75
3 T
1.33 10 17921 PCH4 0.175 1.8T
18400
(10) 2000 0.12 e
T PH2 K eq e [1]
Keq 34173
Pt d p
0.75
3 T
1.33 10 PH 2 S 18557 .7225
PH 2 5.0657
17921
(11) 2000 0.12e T
K eq K eq e T [1]*
Pt d p
CCO C H3 2
equilibrium composition is based on the equation K eq , where
CCH 4 C H 2O
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 Comment Unit Source
9 . 976 10 4
(4) ------ mol/m3s [7]
8 . 83 10 e 5 8 . 315 T
C H 2 CO2
9 . 976 10 4
(5) 8 . 315 T ------ mol/m3s [7]
30 . 9 e C CO C O 2
9 .304 10 5
(6) ------ mol/m3s [7]
3 .552 10 e 11 8 .315 T
C CH 4 C O2
30000
C CO C H3 2
C CH
25014 .0499
1 .987 T 33 .1371
(12) 312 e K eq e mol/m3s [1]*
T
4
K eq C H 2O
PCO
xCO
Pt
e
27760
Fw 2.77 10 xCO x 5 *
CO
1.987 T
1 PCO2 PH 2 mol/[s(g
(13)
P 5553
*
x CO of ash)]
[1]
0.5 t 8.91 Pt K eq PH 2O
Pt 250
e T
7234
3 .6893
K eq e 1 .8 T
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
Table 7. Function of Each Block
Block Model Function
Simulate the coal pyrolysis based on the results of the
PYROLYS RYield
pyrolysis experiment at 1atm
Make pressure correction for the yield of each product from
PRESCORR RYield the pressure in the pyrolysis experiment (i.e. 1atm) to the
pressure in the real gasifier
20 5 Simulation Approach
char are the two main factors affecting the remaining carbon conversion and
product composition.
4rp2
Step 1: R 1
C i RC i
4 3
r p
3
10 3 / 12
Step 2: RC2 i RC1 i
10 6
2
Step 3: RC3 i RC2 i D 1 Vbed
4
Combining above three steps gives the following total conversion expression:
5 Simulation Approach 21
D 2
RC3 i RC i 1 Vbed (15)
16 10 3 rp
Where
D = diameter of gasifier, m.
Vbed = void fraction in gasifier. Vbed 1 V particle , where V particle is particle
V particle
Fcoal t coal
fraction in gasifier. , where Fcoal is coal flow rate; t
4 D 2 h
is residence time of coal in the gasifier; coal is coal density; and h is
gasifier length. Vbed is first calculated in a calculator block called GASIFCAL,
then transferred back to the user kinetics subroutine.
3D 2
R S3 H 2 RS H 2 1 Vbed (16)
128 10 3 rp
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
2
Step 2: Ri2 Ri1 D Vbed
4
Based on the above two steps, the total conversion expression is:
D 2
Ri2 Ri 10 3 Vbed (17)
4
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)
H 2O RCO H 2 O coal
2 1
Step 2: RCO
10 3
H 2 O RCO H 2O
3 2
Step 3: RCO
10 6
2
Step 4:
4
RCO H 2 O RCO H 2O
3
D 1 Vbed
4
Combining above four steps yields the total conversion expression:
D 2
H 2 O RCO H 2 O 1 Ymoisture Yash coal 1 Vbed
4
RCO (18)
4 10 3
Where
5 Simulation Approach 23
Table 8. Stoichiometric Coefficient of H2 in Each Reaction
and Abbreviation of Each Reaction Rate
Stoichiometric Rate of reaction
Reactions
coefficient of H2 (kgmole/ms)
(4) -1 R H2 2 O2
(8) 1 RC3 H 2O
(10) -2 RC3 H 2
(11) -1 R S3 H 2
2
(12) 3 RCH 4 H 2O
4
(13) 1 RCO H 2O
VR = reactor volume.
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
d p u
Re p , 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
b .
s d p2
1 e bt
t
h vs dt
vs ,i
bt
1 e v g vt t (22)
0 b b
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
2 s2,i s2,o
square root, i.e. s , where s ,i and s,o are the solid densities
s2,i s2,o
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.
2
Vg t D h
4
(23)
Where
t = residence time.
h = gasifier length.
Transforming Eq. (23) gives the expression for D:
Vg t
D (24)
h
4
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
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.
5 Simulation Approach 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.
28 6 Simulation Results
Table 12. Operating Condition and Configuration of
Gasifier[1, 5]
Parameter Value Unit
Pressure 24 atm
Length 3.25 m
Diameter 1.5 m
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 built-
in 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
Wen and
Aspen Plus Aspen Plus
Experimental[1] Chaungs
model a model b
model[1]
Parameters
Mole Mole Mole Mole
Flow Flow Flow Flow
fraction fraction fraction fraction
rate rate rate rate
(%, dry (%, dry (%, dry (%, dry
(g/s) (g/s) (g/s) (g/s)
basis) basis) basis) 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
30 6 Simulation Results
70 70
60 60
40 40
30 30
CO
H2
20 20
H2O
CO2
10 10
0 0
0 1 2 3 4 5 6 7 8 9 10
(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:
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
32 7 Conclusions
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.
References 33