You are on page 1of 10

World Academy of Science, Engineering and Technology

International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

Mathematical Simulation of Bubble Column


Slurry Reactor for Direct Dimethyl Ether
Synthesis Process from Syngas
Zhen Chen, Haitao Zhang, Weiyong Ying, Dingye Fang

and other chemicals, and it has an increasing application as


AbstractBased on a global kinetics of direct dimethyl ether ultra-clean fuel for diesel engines and as ozone friendly
(DME) synthesis process from syngas, a steady-state one-dimensional propellant for aerosol industry.
mathematical model for the bubble column slurry reactor (BCSR) has Direct DME synthesis process is in traditional tubular
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

been established. It was built on the assumption of plug flow of gas


fixed-bed reactor, in which the syngas mostly reacted on
phase, sedimentation-dispersion model of catalyst grains and
isothermal chamber regardless of reaction heats and rates for the surface of the solid catalysts. The advantage of this method is
design of an industrial scale bubble column slurry reactor. The high CO conversion and high selectivity for DME. But for
simulation results indicate that higher pressure and lower temperature methanol/ dimethyl ether synthesis is a strongly exothermal
were favorable to the increase of CO conversion, DME selectivity, reaction, it will cause run-away which can detract seriously
products yield and the height of slurry bed, which has a coincidence from the selectivity of catalysts and the catalyst irreversibly
with the characteristic of DME synthesis reaction system, and that the deactivated. So DME direct synthesis has received growing
height of slurry bed is lessen with the increasing of operation
attention in a bubble slurry reactor [1] for its dramatic economic
temperature in the range of 220-260. CO conversion, the optimal
value and theoretical significance for the alleviation of the
operation conditions in BCSR were proposed.
thermodynamics equilibrium limitation of methanol synthesis.
The syngas bubbles are diffused to surface of the catalysts
Keywordsalcohol/ether fuel, bubble column slurry reactor,
global kinetics, mathematical model
through inert medium oil that has high specific thermal
capacity, and then reacted to DME in the three-phase slurry
I. INTRODUCTION reactor. Due to effective heat transfer, the whole reaction bed
can be regard as an isothermal chamber. But the deactivation
C HINA is a country with rich coal, lacking oil and poor gas
and forty percent of crude oil must be imported with the
development of world economy, it is urgent that how to highly
problem of catalysts must be considered for the existence of
water [2] adhering to the surface of catalysts. If the catalyst is
sufficiently active, the capacity of the reactor will be limited by
efficient utilization our coal resource. In recent year, there are the rate of diffusion to or from the catalyst surface.
hot spots to develop new chemical energy technologies in coal
There are normally two types of the catalysts for single-step
industry, such as syngas transformation to methanol/dimethyl
process: bi-functional hybrid catalysts [3]-[4] which are
ether process. Dimethyl ether is an important chemical and
commonly the mechanical mixture of methanol synthesis
intermediate for the production of gasoline, ethylene, aromatics
catalyst (CuO-ZnO-Al2O3) and methanol dehydration catalyst
(-Al2O3/ZSM-5) and liquid slurry catalysts [5] which are
Financial support by a grant from the Major State Basic Research
Development Program of China (973 Program) (No. 2005CB221205). prepared by a novel complete liquid-phase technology and
Zhen Chen was with Department of Light Chemistry and Environment have small and uniform granularity, high dispersion degree,
Engineering, Shandong Institute of Light Industry, Ji'nan Shandong 250353 lower viscosity and higher activity stability. And these slurry
China. He is now with Engineering Research Center of Large Scale Reactor
Engineering and Technology, Ministry of Education, State Key Laboratory of catalysts also contain two types of active sites respectively. The
Chemical Engineering, East China University of Science and Technology, research of DME direct synthesis process is mainly focused on
Shanghai 200237 China (e-mail: chenzhensd@hotmail.com). discrimination of bi-functional catalysts, development of
Haitao Zhang is with Engineering Research Center of Large Scale Reactor
Engineering and Technology, Ministry of Education, State Key Laboratory of
different kinetic models and relevant reactor design of
Chemical Engineering, East China University of Science and Technology, mathematical simulation either in a fixed-bed reactor [6] or
Shanghai 200237 China (e-mail: zht@ecust.edu.com). fluidized bed reactor [7]. Nie et al [8] has been presented an
Weiyong Ying is with Engineering Research Center of Large Scale Reactor
intrinsic kinetics and reactor simulation model for DME direct
Engineering and Technology, Ministry of Education, State Key Laboratory of
Chemical Engineering, East China University of Science and Technology, synthesis from syngas over a bi-functional catalyst of CuO-
Shanghai 200237 China (phone: 86-21-64252193; fax: 86-21-64252192; ZnO-Al2O3 and -Al2O3 in a fixed-bed reactor.
e-mail: wying@ecust.edu.com). In this paper, by fitting our experimental data, a global
Dingye Fang is with Engineering Research Center of Large Scale Reactor
Engineering and Technology, Ministry of Education, State Key Laboratory of kinetic model for liquid phase DME direct synthesis has been
Chemical Engineering, East China University of Science and Technology, proposed subsequently over Cu-Zn-Al-Zr slurry catalyst based
Shanghai 200237 China (e-mail: dyfang@ecust.edu.com).

International Scholarly and Scientific Research & Innovation 4(8) 2010 508 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

on Langmuir-Hinshelwood mechanism. And it has been further explained by the combination of methanol synthesis from CO
developed a steady state one-dimensional mathematical model hydrogenation and from CO2 hydrogenation and methanol
in an industrial scale BCSR based on reasonable assumption dehydration to DME, i.e. (1)-(3).
and simplifications for the design of the reactor. A few
B. Global Kinetics of DME Synthesis
literatures[9] have been published for the kinetics and
mathematical model in BCSR for direct DME synthesis from By choosing CO, CO2 and DME as key components and
syngas over Cu-Zn-Al-Zr slurry catalyst. chemical equation (1), (2), and (3) as reaction system, the
global kinetics equations for methanol synthesis from CO, CO2
II. DEVELOPMENT OF REACTOR MODEL IN BCSR and methanol dehydration to DME based on Langmiur-
Hinshelwood mechanism were expressed as follows
A. Reaction Kinetic Scheme dNCO k1 fCO fH2 2 (1 1)
rCO = = (7)
The main catalytic reactions in direct DME synthesis process dW (1+ KCO fCO + KCO2 fCO2 + KH2 fH2 )3
are considered as follows:
methanol synthesis from CO hydrogenation: dNCO2 k2 fCO2 fH2 3 (1 2 ) (8)
rCO2 = =
CO + 2H 2 CH3OH (1) dW (1+ KCO fCO + KCO2 fCO2 + KH2 fH2 )4
methanol synthesis from CO2 hydrogenation: dN DME k f (1 3 ) (9)
rDME = = 3 M
(1 + K M f M )2
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

CO2 + 3H 2 CH 3OH + H 2O (2) dW


f M f H2O , = f DME f H2O , i
methanol dehydration to DME: fM
where = , =
2CH 3OH CH 3OCH 3 + H 2O (3) 1
K f 1 fCO f H2
2 2
K f 2 f CO2 f H2
3 3
K f3 f M
2

water gas shift reaction (WGS):


refers to the equilibrium degree of the ith independent reaction,
CO + H 2O CO2 + H 2 (4)
respectively, and fj stands for the fugacity of component j,
direct synthesis of DME from CO hydrogenation: which is calculated by the SHBWR equation of state[10]. Kfi is
2CO + 4 H 2 CH 3OCH 3 + H 2O (5) the equilibrium constant in form of each component fugacity
and direct synthesis of DME from CO2 hydrogenation: for the ith independent reactions, and the thermodynamic
2CO2 + 6 H 2 CH 3OCH 3 + H 2O (6) calculation expressions were given by the following relations
[11]
According to the phase law, the number of independent
reactions in the dimethyl ether synthesis process from syngas is
three. So the reaction schemes of DME direct synthesis can be
9203.26
K f1 = exp[13.1652 + 5.92839 ln T 0.352404 10 2 T + 0.102264 10 4 T 2 (10)
T
0.769446 10 8 T 3 + 0.238583 1011 T 4 ] (0.10135) 2
4553.34
K f 2 = exp[1.6654 + 2.72613ln T 1.106294 102 T + 0.172060 104 T 2 (11)
T
1.106294 108 T 3 + 0.319698 1011T 4 ] (0.101325) 2
3204 .71
K f3 = exp[ 9.3932 + + 0.83593 lnT + 2.35267 10 3 T 1.8736 10 6 T 2 (12)
T
+ 5.1606 10 10 T 3 ]
TABLE I
Reaction rate constant as model parameters, namely ki, can REGRESSION PARAMETERS FOR THE GLOBAL KINETICS MODEL
be defined by Arrhenius relations: Pre-exponential Apparent activation energy
Parameters
factors (molg-1h-1) (Jmol-1)
ki = k0i exp(Ei / RT) (i=1, 2, 3) (16) k1 7.704103 26348.74
and the adsorption equilibrium constant, namely Kj, can be k2 8.558102 20587.82
defined by Vant Hoff relations: k3 1.8455102 25845.97
KCO 5.7610-6 -33499.95
Kj = K0 j exp(Ej / RT) (j=CO, CO2, H2, M) (17) KCO2 9.6610-6 -20830.80
where k0i or K0j is the pre-exponential factor, Ei is the apparent KH2 4.30710-2 -20692.27
KM 2.888 -20171.23
activation energy for the ith independent reaction , and Ej is the
apparent adsorption heat for the adsorption equilibrium C. Reactor Model Assumptions
constant of component j.
Zhao [12] has discussed systematically bubble column slurry
According to the total of 25 experimental data shown in
reactor and relevant descriptions in detail of hydromechanics,
Table 1, the parameters values of global kinetic model in
transport processes and mathematical model for commercial
CSTR, with a 95% confidence internal, are listed in Table I.
demonstration plants. The assumption of plug flow in gas phase
is usually valid, but there are two flow patterns for slurry phase:

International Scholarly and Scientific Research & Innovation 4(8) 2010 509 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

fully back-mixing and plug flow. Govindarao [13]-[14]


kS , j aS Ccat (CL, j CS , j ) Ccat i , j ri , j = 0
3
(17)
demonstrated generalized mathematical model in BCSR on the i =1
hypothesis of axial diffusion in gas-liquid-solid phase, Catalyst grains sedimentation-dispersion model can be
boundary heat transfer and grain sedimentation-dispersion expressed by
model for methanol synthesis process. d 2Ccat dCcat (18)
D +u S =0 p
The mathematical model in the BCSR model can be made dZ 2 dZ
further assumptions as follows: Substituting (17) into (16), we can obtain:
d 2C L , j dCL, j
1) Due to the liquid phase inert carrier with high thermal
( )
3
DL uL + k L, j aL CG , j CL, j Ccat i , j ri , j = 0 (19)
conductivity and heat capacity, Bubble column slurry dZ 2
dZ i =1
reactor can be regarded as an isothermal chamber under Further simplification can be made by assuming that the
high turbulence, in which heat transfer can be negligible. Herrys law applies to each gas-liquid phase component.
2) The bubble phase is in plug flow, and gas back-mixing can Combining with the assumptions 2), (15) can be simplified to
be negligible. dCG , j CG , j (20)
3) The liquid phase is assumed to be fully back-mixing flow in uG + k L, j aL CL , j = 0
dZ m
high space velocity and high turbulence.
Comparing to the whole reaction bed, the liquid phase is
4) The components of syngas are sparingly soluble in a liquid non- flowing, then (19) is simplified to
paraffin inert carrier, and then mass transfer resistance of
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

d 2CL, j C 3 (21)
gas phase can be ignored. D L + k a G, j C C r = 0
dZ 2
L, j L m L, j cat i, j i, j

5) Mass transfer resistance was ignored in the liquid-solid i =1

phase, and internal diffusion effectiveness factors of the This mathematical model is based on the global kinetics
catalyst are close to 1 because of adapting to ultrafine slurry model for the catalytic reaction in continuous stirred tank
catalyst. reactor, which take into account the complicated physical
6) Catalyst concentration distribution along the bed height process such as mass transfer and diffusion in the gas-
obeys the grains sedimentation-dispersion model, which liquid-solid three phase. Then (21) can be further simplified to
CG , j 3
take into consideration the influence of both liquid phase k L , j aL = Ccat i , j ri , j
axial back-mixing and grain sedimentation. m i =1

7) Liquid properties, such as gas holdup, mass transfer (22)


coefficient, and diffusion coefficient, are kept constant Substituting Eq. (22) into Eq. (20), we can obtain:
dCG, j 3
along the column bed. uG + Ccat i, j ri , j = 0 (23)
dZ i =1
D.Mathematical Model in BCSR
For the grains sedimentation-dispersion model (18), Smith [15]
Having assumed uniform temperature in the column bed, we provided the simplified calculation equations which is shown
only have to consider material balance equation for component as the following
j in the gas-liquid-solid three phase, which are as follows:
Ccat = Ccat
0
exp(Gx) (24)
The main effect factors of the gas phase concentration-time
history are axial back-mixing of gas phase, superficial gas Combining (23) with (24), the one-dimensional
velocity and gas-liquid mass transfer. In the steady state mathematical model for the three-phase bubble column slurry
conditions, the mass balance equation for the component j in reactor has been established, which was considered to be the
gas phase is given by influence of catalyst grain sedimentation on reaction process
Gas phase: and macro dynamics process.
d 2CG, j dCG, j For the complicated reaction process of alcohol/ether fuel
DG
dZ 2
uG
dZ
( )
kL, j aL CG , j CL, j = 0 (15)
direct synthesis from syngas, we chose methanol synthesis
The main effect factors of the liquid phase concentration- from CO hydrogenation and CO2 hydrogenation and methanol
time history are axial back-mixing of liquid phase, superficial dehydration as the independent reactions, and chose CO, CO2,
liquid velocity, gas-liquid mass transfer and liquid-solid mass and DME as key components. The total transient flux of the gas
transfer. In the steady state, the mass balance equation for the phase in the column can be calculated from the overall material
component j in liquid phase is given by balance.
Liquid phase: NT ,in 1 2 yCO 2 yCO2 (25)
=
d CL, j
2
dCL, j 1 2 yCO,in 2 yCO2 ,in
DL
dZ2
uL
dZ
(
G, j )
+ kL, j aL C CL, j kS, j aSCcat (CL, j CS, j ) = 0 (16) NT
Hence, the transient flux of each key component can be
The main effect factors of the solid phase concentration-time expressed by
history are gas-liquid mass transfer and reaction rate of each 1 2 yCO,in 2 yCO2 ,in
catalytic reaction. In the steady state, the mass balance equation N j = NT ,in y j j=CO, CO2, DME (26)
1 2 yCO 2 yCO2
for the component j in solid phase is given by
Solid phase: Differential equations of (26) are given by

International Scholarly and Scientific Research & Innovation 4(8) 2010 510 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

[( )
dNCO = B 1 2 yCO2 dyCO + 2 yCO dyCO2 ] xTC = 1
(
N out y CO ,out + y CO2 ,out )

[
dNCO2 = B (1 2 yCO )dyCO2 + 2 yCO2 dyCO ] (27) N in (y CO ,in + y CO2 ,in )
dN [( )
DME = B 1 2 yCO 2 yCO2 dyDME + 2 y DME dyCO + dyCO2 ( )] (33)
where and selectivity of DME/methanol is defined as follows
1 2 yCO,in 2 yCO2 ,in 2 N out y DME,out (34)
B = N T ,in S DME =
(1 2 y CO 2 yCO2 ) 2 N in yCO,in N out yCO,out
N out y M ,out (35)
For the direct synthesis process of alcohol/ether fuel, (23) SM =
can be written in the form N in yCO ,in N out yCO ,out
d (u G C G , j )
C cat r j = 0 TABLE II
dl HYDRODYNAMIC AND PHYSICAL PROPERTY CORRELATIONS
(positive j=CO, CO2, negative j=DME) (28 Relevant parameters Correlations
)
Nj Initial mass C cat
0
= C cat G [exp (G ) 1 .0 ]
Considering CG , j = , substituting (22) into (28), and
concentration of
AuG where:
catalyst in the gas G = Lu p Lh DS
integrating, the differential equations of material balance for inlet ,
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

each key components in BCSR was given by L = 1 Ccat p


u p = 1.10 u G0.026 u t0.80 3.5
dy C O = M T (1 2 y C O ) rC O 2 y C O rC O 2
L

dl f
1 2 yC O 2 yC O2 Grain sedimentation gd p2 ( p L )
(29 ut =
velocity ut[16]: 18 L
dy
( )
1 2 y C O rC O 2 y C O rC O
uG DR
= M T f = 9.6 ( Fr 6 Re g )
C O2 Solid phase

2 2 2 0.1114
+ 0.019 Re1.1
dl 1 2 yC O 2 yC O2 dispersion coefficient DS p

DS[15]:
( )
where:
dy D M E rD M E + 2 y D M E rC O + rC O
Fr = uG ( gDR )
0.5
= M T f 2

dl y y

1 2 2
CO CO2
Re p = ut d p L L
) Re g = uG DR L L
where
C cat A
Gas holdup G
[17]
: G = 0.5863uG0.5159Wcat0.2454 L0.0073 0.1403
M = Density of liquid
L = 171.0 0.1677 (1T )
2/7
1 2 y CO ,in 2 y CO2 ,in r

N T ,in paraffin oil L[18]:


(1 2 y CO 2 yCO2 )2 where:
Tr = T / 916.18
Substituting global kinetics equations and (24) into (29), the Viscosity of paraffin
set of the differential equations (29) can be solved by the four- oil L:
ln L = 3.0912 + 1.7038 10 3 / T
order Runge-Kutta-Felhberg numerical integration method Surface tension of
L = 50.7657 0.0737 T
paraffin oil :
using the following boundary condition.
at the inlet of the BCSR (l=0):
y CO = y CO ,in , y CO = y CO ,in , y DME = y DME,in
2 2
III. RESULTS AND DISCUSSION
Combining with the material balance, numerical solutions of Using the simulation calculation program that we developed,
the molecule fraction of each component in the outlet of the the behavior of reactor design was carried out for DME direct
BCSR are obtained. The determination of hydrodynamic and synthesis from syngas in the bubble column slurry reactor of
physical property correlations is listed in Table II. 10, 000t/a dimethyl ether under the typical industrial operating
For the coexistence of parallel hydrogenation of CO, CO2 conditions that were as following: the feed composition of
and water gas shift reaction, CO2 was considered as either the coal-based syngas: yH2 = 0.70, yN2 = 0.10, yCO = 0.15, yCO2 =
reactants or products in different operation conditions and 0.05; reaction temperature: 240 , reactor pressure: 5MPa,
different syngas composition, the total carbon conversion and reactor diameter: 0.8m, catalyst content: 30%(wt), gas
selectivity of DME/methanol were used for the purposes of volumetric flux: 10000 Nm3h-1. Meanwhile, it is also discussed
quantitative determination of the effect of the operation in detail the influence of operation conditions and reactor
conditions (temperature, pressure and weight hourly space diameter on reaction results with simulation results of the
velocity) on slurry catalyst. Given that the content of reactor design.
hydrocarbons as byproducts can be negligible, on the basis of
feed and product flow rates and carbon balance, the total carbon A. Axial Distribution of Catalyst Grain
conversion should be defined by 1. Effect of Particles Diameter
Simulation results of catalyst axial concentration distribution
were be carried out by varying the catalyst grain diameter in the
range of 0.05-0.20mm, and maintaining the remaining

International Scholarly and Scientific Research & Innovation 4(8) 2010 511 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

operating variables constant at the following values: reaction 400


temperature, 513K; reactor pressure, 5MPa; reactor diameter, 20%

Catalyst Concentration (kg/m )


25%

3
0.8m; catalyst content, 30%(wt); superficial gas velocity, 350
30%
0.1973ms-1. As be observed from Fig.1, the influence of 35%
catalyst particles diameter on the catalyst axial concentration 300
distribution along the bed height is very important. The catalyst
250
concentration distribution becomes well-distributed with the
decreasing of particles diameter, and is almost uniform when 200
the particles diameter is 0.05mm. This is due to the dual role of
drag force of bubble phase on catalyst grains and sedimentation 150
rate of catalyst grains in slurry phase which is increased with
100
the increasing particles diameter, neglecting the influence of
density of different catalysts. 0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless Height
Fig. 2 Effect of catalyst content on catalyst axial concentration
0.05mm
360 0.10mm
Catalyst Concentration (kg/m )

3. Effect of Superficial Gas Velocity


3
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

0.15mm
320 0.20mm The results of the catalyst axial concentration distribution
were be carried out by varying superficial gas velocity in the
280 range of 0.1142-0.2388 m/s, and the remaining operating
conditions have been maintained constant at the following
240
values: reaction temperature, 513K; reactor pressure, 5MPa;
200
reactor diameter, 0.8 m; catalyst content, 30%(wt). As can be
seen from Fig.3, the tendency of the catalyst axial
160 concentration distribution is gradually close to uniform with the
increasing of superficial gas velocity. It is a reasonable
0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless Height
explanation that the drag force of bubble phase on catalyst
grains increases with the increasing superficial gas velocity,
Fig. 1 Effect of particles diameter on catalyst axial concentration and then sedimentation velocity of catalyst particles is slow
2. Effect of Catalyst Content down, which could lead to well distribution of catalyst axial
The effect of catalyst content on the catalyst axial concentration. It also can be obtained from Fig.3 that the
concentration distribution is shown in Fig.2. The result varying of the superficial gas velocity has slightly influence on
correspond to catalyst grain diameter of 0.060mm and the the catalyst axial concentration distribution.
remaining operating conditions have been maintained constant
at the following values: reaction temperature, 513K; reactor 270
0.1142m/s
pressure, 5MPa; reactor diameter, 0.8m; superficial gas
Catalyst Concentration (kg/m )
3

265 0.1557m/s
velocity, 0.1973ms-1. It has been observed that the tendency of 0.1973m/s
260 0.2388m/s
the catalyst axial concentration distribution is almost uniform
for the ultrafine catalysts grains of 0.060mm average diameter 255
with the increasing of catalyst content in the range of
250
20%-35%(wt), the influence of catalyst content on the catalyst
axial concentration distribution has been not obvious. Hence 245
the DME direct synthesis process can be carried out under the 240
slurry catalyst with a higher mass content to achieve higher
methanol/DME yield. 235
0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless Height
Fig. 3 Effect of superficial gas velocity on catalyst axial concentration
4. Effect of Reactor Diameter
The effect of reactor diameter on the catalyst axial
concentration distribution along the bed height is shown in
Fig.4. The result correspond to catalyst grain diameter of
0.060mm and the remaining operating conditions have been
maintained constant at the following values: reaction
temperature, 513K; reactor pressure, 5MPa; catalyst content,

International Scholarly and Scientific Research & Innovation 4(8) 2010 512 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

30%(wt). From Figures 4, it is confirmed that the varying of the 270


reactor diameter has heavily influence on the catalyst axial 3MPa
265

Catalyst Concentration (kg/m )


concentration distribution. In this case, superficial gas velocity

3
4MPa
and operating bed height are main factors influencing 5MPa
260 6MPa
distribution uniformity. Kept gas normal volumetric flux in the 7MPa
255
inlet of BCSR constant, superficial gas velocity and operating
bed height will be rapidly increased with the decreasing of 250
reactor diameter because both of them are inversely 245
proportional to quadratic power of reactor diameter.
Meanwhile, because the effect of superficial gas velocity is 240
slightly in coalesced bubble regime which has been previously 235
discussed, a sharp increasing of operating bed height will be
230
aggravated non-uniform distribution of catalyst axial 0.0 0.2 0.4 0.6 0.8 1.0
concentration, especially in the slugging regime which is Dimensionless Height
caused by high superficial gas velocity and minor reactor
Fig.5 Effect of reactor pressure on catalyst axial concentration
diameter.
6. Effect of Reaction Temperature
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

The effect of reaction temperature on the catalyst axial


360 0.2m concentration distribution is shown in Fig.6. The result
Catalyst Concentration (kg/m )
3

0.3m
0.4m
correspond to catalyst grain diameter of 0.060mm and the
320 remaining operating conditions have been maintained constant
0.6m
0.8m at the following values: reactor pressure, 5MPa; reactor
280 diameter, 0.8m; catalyst content, 30%(wt). The influence of
reaction temperature should be discussed from the following
240 two aspects: one is that physical properties of liquid paraffin
(viscosity and density) are function of reaction temperature,
200 and both of them are reduced with the increasing of the reaction
temperature, which can lead to the nonuniformity of catalyst
160
particles axial concentration distribution; another is that
0.0 0.2 0.4 0.6 0.8 1.0 superficial gas velocity in bubble column bed is increased with
the increasing of the reaction temperature, which can improve
Dimensionless Height
the uniformity of catalyst particles axial concentration
Fig.4 Effect of reactor diameter on catalyst axial concentration distribution. By taking the two aspects into consideration, the
5. Effect of Reactor Pressure reaction temperature has little or no influence on the catalyst
The effect of reactor pressure on the catalyst axial axial concentration distribution.
concentration distribution is shown in Fig.5. The result
270
correspond to catalyst grain diameter of 0.060mm and the 220
Catalyst Concentration (kg/m )
3

remaining operating conditions have been maintained constant 230


at the following values: reaction temperature, 513K; reactor 240
260
250
diameter, 0.8m; catalyst content, 30%(wt). It can be obtained 260
that the decreasing of the reactor pressure has slightly effect on
250
the catalyst axial concentration distribution uniformity. Gas
normal volumetric flux remaining unchanged, superficial gas
velocity will be increased with the decreasing of reactor 240
pressure, and then improve axial uniform distribution of
catalyst particles. By comparing and analyzing factor trend in
230
the Fig.3 and Fig.5, it is clear that a similar trend by the
decreasing of reactor pressure or the increasing of superficial 0.0 0.2 0.4 0.6 0.8 1.0
gas velocity. Dimensionless Height
Fig. 6 Effect of reaction temperature on catalyst axial concentration
B. Discussion of Model Simulation Results
1. Effect of Reaction Temperature
The influence of reaction temperature on static bed height
and slurry operating bed height with model simulation results
in BCSR is shown in Fig.7, and the effect of reaction

International Scholarly and Scientific Research & Innovation 4(8) 2010 513 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

temperature on total carbon conversion and selectivity of DME


12
and on production capacity of products with model simulation
results in BCSR are shown in Fig.8- Fig.9, respectively. As can

Production capacity (10 t/a)


10
be seen, the total carbon conversion, selectivity and yield of

-3
DME decrease slightly with increasing temperature in the range
8
of 220-260 , which is in accordance with thermodynamic
methanol
characteristic that higher temperatures is unfavorable to 6 DME
equilibrium conversion of syngas since DME direct synthesis
reaction is an exothermic reaction. And it is found that each 4
reaction is close nearly to the state of chemical equilibrium by
comparison between experimental and simulation values of 2
equilibrium constants of each reaction in the outlet of the
reactor. It can be obtained from Fig.7 that the static bed height 0
220 230 240 250 260
and operating bed height drop suddenly as the temperature
increases, even though the average gas holdup and superficial Temperature ( )
space velocity dont change obviously. This is the result that Fig. 9 Effect of reaction temperature on production capacity
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

the reaction rate of each product is improved with increasing


2. Effect of Reactor Pressure
temperature. By taking into consideration the combination of
The influence of reactor pressure on the static bed height
economic benefits of dimethyl ether and equipment investment
and the slurry operating bed height with model simulation
of bed height, it is advised that the optimal reaction temperature
results in BCSR is shown in Fig.10, and the effect of reactor
should be about 240 in the DME synthesis process. pressure on total carbon conversion and selectivity of DME and
on production capacity of products with model simulation
results in BCSR are shown in Figures 11 and 12, respectively. It
22 L, static bed height is confirmed that total carbon conversion, selectivity of DME
Lh, operating bed height
and yield of methanol/DME are all increased as reactor
20 pressure increases in the range of 3-7Mpa, which is based on
the fundamentals that increasing pressure is favorable to DME
Bed Height (m)

18 direct synthesis process for stoichiometric-number-reducing


reaction. It is obvious that when the reactor pressure is
16 increased, average gas holdup and superficial space velocity
are declined obviously. As a result, the operating bed height is
14 decreased greatly, while the static bed height decreases slightly.
It seems that higher pressure is favorable to DME direct
12 synthesis process with all simulation results, but considering
that the slurry reactor is also a pressure vessel, it is rather high
220 230 240 250 260
of equipment investment, operation cost and energy
Temperature ( ) consumption in this case. It is proposed that 5MPa is the
Fig.7 Effect of reaction temperature on bed height optimal reactor pressure of DME synthesis process for
commercial scale.
1.0
21
20 L, static bed height
0.8
Lh, operating bed height
Total Carbon Conversion

19
and Selectivity of DME

0.6 18
Bed Height (m)

17
0.4
16
15
0.2 xTC, total carbon conversion
SDME, selectivity of DME 14

0.0 13
220 230 240 250 260
12
Temperature ( ) 3 4 5 6 7
Pressure (MPa)
Fig. 8 Effect of reaction temperature on total carbon conversion and
selectivity of DME Fig. 10 Effect of reactor pressure on bed height

International Scholarly and Scientific Research & Innovation 4(8) 2010 514 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

1.0
40
L, static bed height
35 Lh, operating bed height
0.8
Total Carbon Conversion
and Selectivity of DME

30

Bed Height (m)


0.6 25

20
0.4
15

0.2 10
xTC, total carbon conversion
SDME, selectivity of DME 5
0.0 0
3 4 5 6 7 0.6 0.7 0.8 0.9 1.0
Pressure (MPa) Reactor Diameter (m)
Fig.11 Effect of reactor pressure on total carbon conversion and Fig. 13 Effect of reactor diameter on bed height
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

selectivity of DME
1.0
12

0.8
Production capacity (10 t/a)

10
Total Carbon Conversion
and Selectivity of DME
-3

8 0.6

methnaol
6 DME 0.4

4 0.2 xTC, total carbon conversion


SDME, selectivity of DME
2
0.0
0.6 0.7 0.8 0.9 1.0
0
3 4 5 6 7 Reactor Diameter (m)
Pressure (MPa) Fig. 14 Effect of reactor diameter on total carbon conversion and
selectivity of DME
Fig. 12 Effect of reactor pressure on production capacity
3. Effect of Reactor Diameter 12
The influence of the reactor diameter on the static bed height
and the slurry operating bed height with model simulation 10
Production capacity (10 t/a)

results in the BCSR is shown in Fig.13, and the effect of the


-3

reactor diameter on total carbon conversion and selectivity of 8


DME and on production capacity of products with model
methanol
simulation results in BCSR are shown in Fig.14-Fig.15 6 DME
respectively. As is observed, total carbon conversion,
selectivity of DME, and yield of methanol/DME are kept 4
almost constant with a reactor diameter in the range of 0.6-1.0
m. But both the operating bed height and the static bed height 2
are increased obviously because the average gas holdup and
superficial space velocity are increased as the reactor diameter 0
0.6 0.7 0.8 0.9 1.0
decreases. Considering the double influences of the diameter
and the height of the reactor on unit investment, the reactor Reactor Diameter (m)
diameter of 0.8m was suggested to aim at a suitable ratio of Fig. 15 Effect of reactor diameter on production capacity
height to diameter for the reactor design of DME direct
synthesis process. IV. CONCLUSION
A steady-state one-dimensional mathematical model for
three-phase bubble column slurry reactor has been established
based on the assumptions of plug flow of gas phase, catalyst

International Scholarly and Scientific Research & Innovation 4(8) 2010 515 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

grains sedimentation-dispersion model and isothermal process reaction i


p: density of catalyst particles, kgm-3
in the whole reactor bed. It is discussed in detail the influence Superscripts:
of operation conditions on catalyst axial concentration *: indicate equilibrium value
distribution with simulation results based on 0: indicate initial value
Subscripts
sedimentation-dispersion model, from which it can be obtained
cal: calculated value
that the particle diameter and reactor diameter are the main two cat: catalyst
factor influencing concentration distribution uniformity. exp: experimental value
The influence of the construction parameters of the reactor G: gas phase
in: at the inlet of reactor bed
and operation parameters of DME synthesis industrial L: liquid phase
demonstration unit was also determined. It can be obtained that out: at the outlet of reactor bed
higher pressure and lower temperature were beneficial to the P: catalyst particles
S: solid phase
increase of CO conversion, DME selectivity and products T: total
yield, and that height of slurry bed is lessen with the increasing WGS: water-gas shift reaction
of operation temperature in the range of 220-260 . The
REFERENCES
optimal operation conditions in BCSR were proposed:
[1] K. D. P. Nigam, A. Schumpe, Three-phase Sparged Reactors. London:
temperature at 240, pressure at 5MPa and reactor diameter of Gordon and Breach Science Publishers, 1996, ch. 5-6, pp. 339-422.
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

[2] A. T. Aguayo, J. Erea, I. Sierra, M. Olazar, J. Bilbao, Deactivation and


0.8m.
regeneration of hybrid catalysts in the single-step synthesis of dimethyl
ether from syngas and CO2, Catalysis Today, vol. 106, no. 1-4, pp.
NOMENCLATURE 265270, Oct. 2005.
[3] J. Erea, R. Garoa, J. M. Arandes, A.T. Aguayo, J. Bilbao, Effect of
A: reactor bed cross-sectional area, m2
operating conditions on the synthesis of dimethyl ether over
aL: specific surface area of gas-liquid mass transfer, m2m-3
CuO-ZnO-Al2O3/NaHZSM-5 bifunctional catalyst, Catal. Today, vol.
aS : specific surface area of particles, m2m-3
107-108, pp. 467-473, Oct. 2005.
Ccat: catalyst mass concentration in slurry phase, kgm-3
[4] A.T. Aguayo, J. Erea, D. Mier, J. M.Arandes, M. Olazar, J. Bilbao,
Ccat : average mass concentration of catalyst in reactor, kgm-3 Kinetic modeling of dimethyl ether synthesis in a single step on a
Ccat
0 :
initial mass concentration of catalyst in the gas inlet, kgm-3 CuO-ZnO-Al2O3/-Al2O3 catalyst, Ind. Eng. Chem. Res., vol. 46, no. 17,
pp. 5522-5530, July. 2007.
CG , j : concentration of gas phase component j, kmolm-3 [5] Z.-H. Gao, W. Huang, J.-Y. Wang, L.-H. Yin, K.-C. Xie, Complete
: equilibrium concentration of gas phase component j at liquid-phase preparation and characterization of Cu-Zn-Al-Zr slurry
C G, j
gas-liquid interface, kmolm-3 catalysts for synthesis of dimethyl ether, Acta Chimica Sinica, vol. 66,
CL, j : concentration of liquid phase component j, molm-3 no. 3, pp. 295-300, Feb. 2008.
concentration of liquid phase component j on the surface of [6] D. Song, W. Cho, G. Lee, D. K. Park, E. S. Yoon, Numerical analysis of
CS , j : a pilot-scale fixed-bed reactor for dimethyl ether (DME) synthesis, Ind.
catalyst, kmolm-3
D R: internal diameter of BCSR, m Eng. Chem. Res., vol. 47, no. 13, pp. 4553-4559 May. 2008.
DG: axial back-mixing diffusion coefficient in gas phase, m2s-1 [7] W.-Z. Lu, L.-H. Teng, W.-D. Xiao, Simulation and experiment study of
DL: axial back-mixing diffusion coefficient in slurry phase, m2s-1 dimethyl ether synthesis from syngas in a fluidized-bed reactor, Chem.
DS: axial dispersion coefficient of catalyst particles, m2s-1 Eng. Sci., vol. 59, no.22-23, pp.5455-5464, Nov-Dec. 2004.
dp : average diameter of catalyst particles, m [8] Z.-G. Nie, H.-W. Liu, D.-H. Liu, W.-Y. Ying, D.-Y. Fang, The global
fj: fugacity of component j, Pa kinetics of synthesis of dimethyl ether from syngas containing N2 over
G: gravitational acceleration, ms-2 bifunctional catalyst, Chemical Reaction Engineering and Technology,
liquid mass transfer coefficient of component j at gas-liquid vol. 20, no. 1, pp. 1-7, Mar. 2004.
kL,j: [9] D.-H. Liu, X. Hua, D.-Y. Fang, Mathematical Simulation and Design of
interphase, ms-1
liquid mass transfer coefficient of component j at liquid-solid three-phase bubble column reactor for direct synthesis of dimethyl ether
kS,j: from syngas, Journal of Natural Gas Chemistry, vol. 16, no.2, pp.
interphase, ms-1
L: static bed height, m 193-199, Apr. 2007.
Lh : slurry operating bed height, m [10] W.-D. Song, B.-C. Zhu, Z.-C. Luo, L.-B. Yu, G.-X. Feng, X. Xu,
m: gas-liquid equilibrium constant Computation for heat of reaction and equilibrium constant of methanol
Nj: transient flux of component j in reactor bed, mols-1 synthesis under pressure by using SHBWR equation of state, Journal of
NT: transient flux of gas in reactor bed, mols-1 East China University of Science and Technology, vol. 17, no. 1, pp.
NT,in: inlet flux of syngas, mols-1 11-24, Jan. 1981.
[11] Q. Zhang, J. Yang, W.-Y. Ying, D.-Y.Fang, Calculation of equilibrium
reaction rate of component j involved in chemical reaction i
ri,j: conversion and selectivity for dimethyl ether synthesis from syngas,
kmolkg-1s-1 Chemical Engineering, vol. 33, no. 2, pp. 64-68, Apr. 2005.
rj: reaction rate of component j, kgm-1s-1 [12] Y.-L. Zhao, Mathematical model for bubble column slurry reactor,
R: gas constantkJkmol-1K-1 Chemical Engineering, vol. 19, no. 5, pp. 13-21, Oct. 1991.
SDME: selectivity of dimethyl ether [13] V. M. H. Govindarao, On the dynamics of bubble column slurry
T: reaction temperature, K reactors, Chem. Eng. J., vol. 9, no. 3, pp. 229-240, June. 1975.
u G: superficial gas velocity, ms-1 [14] V. M. H. Govindarao, M. Chidambaram, Semibatch bubble-column
Vcat: volume fraction of catalyst in slurry phase without syngas in slurry reactors: effect of dispersion on the steady-state behavior, AIChE
W: weight of catalyst, kg J., vol. 30, no. 5, pp. 842-845, Sept .1984.
Wcat: mass fraction of catalyst particles in slurry phase, w.% [15] D. N. Smith, J. A. Ruether, Dispersed solid dynamics in a slurry bubble
yj: mole fraction of component j in gas phase column, Chem. Eng. Sci., vol. 40, no. 5, pp. 741-754, May. 1985.
WGS: equilibrium degree of water-gas shift reaction [16] M.-H. Chen, Principles of Chemical Industry (volume two). Beijing:
Chemical Industry Press, 2000, ch. 5, pp. 197.
G: gas holdup [17] B.-Q. Ding, J.-B. Zhang, D.-Y. Fang, B.-C. Zhu, Hydrodynamic study of
i,j: stiochoimetric coefficient of component j involved in chemical three-phase slurry reactor with high solid concentration, Journal of East

International Scholarly and Scientific Research & Innovation 4(8) 2010 516 scholar.waset.org/1999.2/5141
World Academy of Science, Engineering and Technology
International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:4, No:8, 2010

China University of Science and Technology, vol. 26, no. 3, pp. 22-231,
June. 2000.
[18] H.-F. Qin, S.-R. Wang, B.-Q. Ding, B.-C. Zhu, Determination and
estimation of physical property data for liquid paraffin, Natural Gas
Chemical Industry, vol. 24, no. 3, pp. 56-58, June. 1999.
International Science Index, Chemical and Molecular Engineering Vol:4, No:8, 2010 waset.org/Publication/5141

International Scholarly and Scientific Research & Innovation 4(8) 2010 517 scholar.waset.org/1999.2/5141