Chemical Engineering & Processing: Process Intensification 122 (2017) 172–180

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Chemical Engineering & Processing: Process Intensification

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Dimethyl ether synthesis in a multi-stage fluidized bed reactor T

M.E.E. Abashar
Department of Chemical Engineering, College of Engineering, King Saud University, PO Box 800, Riyadh 11421, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: The two-phase model with verified reaction kinetics has been implemented to study numerically dimethyl ether
Dimethyl ether (DME) production in a novel multi-stage fluidized bed catalytic reactor. The single-bed configuration results
Fluidized bed reactor show that the bifunctional catalyst composition [CuO–ZnO–Al2O3/HZSM-5] has a pronounced impact on en-
Modeling hancing the reactor performance. Also, the simulation results indicated that the two-bed configuration gives a
Multi-stage
substantial enhancement of DME yield of 32.67% compared to the single-bed configuration. This yield im-
Simulation
provement is also accompanied by significantly improved DME selectivity of almost 100%. The complex in-
teractions of the bifunctional catalyst composition, feed composition and multi-stage configuration play a central
role in the extent of the synergy. Interesting two types of maximum phenomena are observed and explanations
have been offered. It seems that synergistic effects have kinetics and thermodynamic strong impact on the
development of these phenomena. The loci of these maxima are significant for optimal design and control of
multi-bed configurations. It appears that application of multi-stage fluidized bed catalytic reactors is highly
promising in DME industry.

1. Introduction synthesis from syngas. The syngas is usually obtained from natural gas,
coal or biomass [10]. However, the natural gas is still the predominant
Today, the world faces great challenges of energy and environment. source of the syngas due to its abundance availability. A metallic Cu-
These topics are the most concerning problems for scientists, engineers based catalyst such as CuO–ZnO–Al2O3 is employed in this step
and industry. Now, it becomes evident that dimethyl ether (DME) as a [1,5,11–14]. Two catalytic reactions take place as follows:
synthetic fuel has a promising potential to substitute the automobiles Methanol synthesis:
diesel fuel owing to its attractive characteristics such as [1–7]: it is an
CO2 + 3H2 ⇌ CH3 OH + H2 O [ΔH298 = −49.50 kJ /mol]
oxygenated simple ether (CH3OCH3, 34.78 wt% O2) with a high cetane
(1)
number (50–60), a clean fuel free from SOx, less engine noise, easy to
store and transport. Also, can be used as an alternative fuel for the Water-gas shift reaction (WGS):
liquefied petroleum gases (LPG) because its physical properties are al-
CO + H2 O ⇌ H2 + CO2 [ΔH298
most similar to the LPG. DME has considerable potential to be used as a
fuel for fuel cells. Furthermore, DME can be used as a refrigerant and an = − 41.13 kJ /mol ] (2)
aerosol propellant instead of ozone harmful chemicals such as chloro- And, the net rate of reaction is given by:
fluorocarbons (CFCs). In the chemical industry, DME can be utilized as
a feedstock to produce many important chemicals such as hydrogen, CO + 2H2 ⇌ CH3 OH [ΔH298
methyl acetate, acetic acid, light olefins and dimethyl sulfate. The in- = − 90.63 kJ /mol ] (N1)
creased worldwide demand for DME has imposed a wide range of
It is obvious that, the reactions are dependent. The second step is
challenges on academia and industry to improve the DME existing
methanol dehydration to DME using a solid acidic catalyst such as
technology. Among the key challenges are the reactor design, catalysts
HZSM-5 (Protonated Zeolite Socony Mobil-5) or γ-Al2O3 (silica-alu-
and kinetics. In fact, many big companies such as Total, Amoco, Mit-
mina) [1,7,15,16]. Zeolite based catalysts due to their tunable acidity
subishi Co, Haldor Topsøe and Navistar International Corp. are inter-
and stability have gained numerous advantages over alumina catalysts
ested in the development of DME production technology [3,8]. Two
with respect to catalyst deactivation [4,17,18]. Moreover, zeolites al-
processes are used to produce DME, the indirect and direct process [9].
lows low-temperature operation and hence the suppression of coke
The indirect process is conventionally used to produce DME and called
deposition and catalyst sintering [18]. Also, zeolite based catalysts are
a two-step process. The first step of this route involves methanol

E-mail address: [email protected].

http://dx.doi.org/10.1016/j.cep.2017.09.018
Received 9 February 2017; Received in revised form 17 July 2017; Accepted 30 September 2017
Available online 16 October 2017
0255-2701/ © 2017 Elsevier B.V. All rights reserved.
M.E.E. Abashar Chemical Engineering & Processing: Process Intensification 122 (2017) 172–180

Nomenclature K1 Equilibrium constant of reaction (1), bar−2

K2 Equilibrium constant of reaction (2), [−]
A Cross-sectional of the reactor, m2 K3 Equilibrium constant of reaction (3), bar
Ab Cross-sectional occupied by the bubble phase, m2 (Kbc)i Mass transfer coefficient of component i (bubble phase-
Ar Archimedes number, [−] cloud phase), s−1
Cib, Cid Concentration of component i in the bubble and dense (Kcd)i Mass transfer coefficient of component i (cloud phase-
phases respectively, kmol m−3 dense phase), s−1
CiF Concentration of component i in the feed, kmol m−3 (Kbd)i Overall mass transfer coefficient of component i (bubble
db Bubble diameter, m phase-dense phase), s−1
dbm Maximum bubble diameter, m Mi Molecular mass of component i, kg/kmol
dbo Bubble diameter just above the distributor, m Pi Partial pressure of component i, bar
dP Mean particle diameter, m P Total pressure, bar
D Reactor diameter, m R Ideal gas constant, kJ/kmol K
Dij Molecular diffusivity of component i in component j, Ri Rate of reaction i, kmol kg−1 s−1
m2 s−1 T Temperature, K
Dij Molecular diffusivity of component i in component j, Ub Velocity of a bubble rising through a bed, m s−1
m2 s−1 Uo Superficial gas velocity, m s−1
Dim Molecular diffusivity of component i in gas mixture, Umf Superficial gas velocity at minimum fluidizing conditions,
m2 s−1 m s−1
Fi Molar flow rate of component i in the feed, kmol s−1 yi Mole fraction of component i, [−]
g Acceleration of gravity, m s−2 Yi Dimensionless concentration of component i, [−]
Gb, Gd Gas volumetric flow rate in the bubble and dense phase Z Dimensionless reactor height, [−]
respectively, m3 s−1
h Bed height, m Greek symbols
H Total bed height, m
Hmf Bed height at minimum fluidizing condition, m γij Stiochiometric coefficient of component i in the jth reac-
-ΔHi Heat of reaction i, kJ mol −1 tion
k1 Reaction rate constant of reaction (1), kmol εmf Bed voidage at minimum fluidizing condition, [−]
bar−2 kg−1 s−1 δ Volume fraction of the catalyst bed occupied by the bubble
k2 Reaction rate constant of reaction (2), kmol phase respectively, [−]
bar−1 kg−1 s−1 θ1, θ2 Mass fraction of catalyst 1 and 2 respectively, [−]
k3 Reaction rate constant of reaction (3), kmol μg Gas viscosity, kg m−1 s−1
bar−1 kg−1 s−1 ρg Gas density, kg m−3
KCO2, KCO, KH2 Adsorption constant for H2, CO2 and CO respec- ρP Solid particle density, kg m−3
tively, bar−1

found to have good resistance to water poisoning [17,18]. The fol- significant.
lowing catalytic methanol dehydration reaction occurs in this step: In recent years, the competitive advantages of the direct method
Methanol dehydration reaction: have attracted increasing attention to this process. Different types of
reactors such as slurry reactors, fixed bed reactors and fluidized bed
2CH3 OH + ⇌ CH3 OCH3 + H2 O [ΔH298 = − 23.56 kJ /mol ]
reactors are involved in DME synthesis by this method. A comprehen-
(3) sive review of DME reactors has been given by Azizi et al. [7]. Lu et al.
And, the net rate of reaction is given by: [1] have reported that the fluidized bed catalytic reactor for DME
synthesis shows better performance than the slurry and fixed bed re-
3 CO + 3H2 ⇌ CH3 OCH3 + CO2 [ΔH298 = − 245.95 kJ / mol ] actors. The comparison based on CO conversion, DME selectivity and
(N2) productivity (XCO,SDME, PDME), respectively. The results reported as
follows: the slurry reactor gives (17%, 70%, 0.2 g/g/h) [27]; the fixed
It is obvious reaction (1), (2) and (3) are not independent. The re-
bed reactor gives (10.7,91.9,0.5 g/g/h) [28]; and fluidized bed reactor
actions are reversible and exothermic and subjected to thermodynamic
gives (48.5%,97%,0.45 g/g/h) [1]. As it can be seen that, the super-
limitations. The steps of this method are in series and can be separated
iority of the fluidized is obvious. Moreover, the fluidized bed reactor
or integrated. The separated steps are more costly since the dehydration
has attractive features among them: (a) good mixing enables to achieve
step is affected by the price and availability of methanol [19,20].
isothermality and temperature control; (b) negligible diffusion limita-
The direct method is called a single-step method. In this method,
tions due to fine particles used; (c) low pressure drop; (d) large amount
syngas to dimethyl ether (STD) occurs in a single reactor using a bi-
of catalyst can be used; (e) easy to circulate the catalyst for regenera-
functional catalyst. The methanol synthesis and dehydration catalysts
tion.
e.g. (CuO–ZnO–Al2O3/HZSM-5) are combined to form the bifunctional
To the best of our knowledge, the application potential of multi-
catalyst. Different bifunctional catalyst preparation techniques have
stage fluidized bed reactors for production of DME has been scarcely
been reported by numerous investigators [1,2,12,21–26]. This pro-
investigated in the literature. Therefore, the purpose of this investiga-
mising field is still faces many challenges. The two catalytic sites of the
tion is to explore by mathematical modeling and simulation the po-
bifunctional catalyst allow reactions (1)–(3) to occur simultaneous for
tential and advantages that can be gained by implementing the multi-
in-situ consumption and formation of the components with a strong
stage concept to the fluidized bed reactor for direct DME synthesis from
synergy. This synergy between the reactions plays an important role in
syngas. Here, we considered various catalyst compositions at constant
the displacement of the thermodynamic equilibriums and gives higher
total catalyst load to evaluate the performance of the reactor. The re-
syngas conversion and DME yield compared to the indirect method
actor performance is analyzed and the distinctive features of different
[1,5,27]. Furthermore, the cost reduction by the direct method is

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catalyst bed configurations are investigated. It is essential to study these CO2 as a precursor to methanol and CO is converted to CO2 by the water
features in order to understand how to properly implement the optimal gas shift reaction. The enhancement and inhibitory effects of CO2 as-
catalyst bed configurations in the design and operation of these types of cribed to water formed by hydrogenation of CO2. At low concentrations
important reactors. of CO2, the water consumed by the water gas shift reaction favors both
reactions. At high concentrations of CO2 the excessive water causes site
2. Reaction kinetics blockage, decreasing catalyst activity. This view is supported by two
reaction mechanisms of Lu et al. [1] and Bussche & Froment [14] and
Despite the fact that extensive literature has been published on presented in Table 1. Surprisingly, the kinetic model based on this view
methanol synthesis over the copper-zinc oxide catalysts, the in- able to predict satisfactory the experimental data reported by Klier et al.
vestigators overwhelmed by the complexity of the subject and fail to [29]. Despite differences in views, the reported results agreed on the
provide an articulated unified kinetic model. The kinetics models re- observed phenomena of the enhancement effect of methanol synthesis
ported in the literature show different views for the methanol synthesis rate at small concentrations of CO2 and the inhibitory effect of water at
from H2: CO mixture. Klier et al. [29] considered CO is the main source high concentrations [3].
of carbon in methanol and small concentrations of CO2 have promotion The reaction kinetics developed by Lu et al. [1] over a bifunctional
effect attributed to its ability to oxidize Cu0 to Cu+, increasing catalyst catalyst composed of catalyst 1 (CuO-ZnO–Al2O3) and catalyst 2
activity. And, the inhibitory effect at high concentrations of CO2 owing (HZSM-5) for DME synthesis in a bubbling fluidized bed reactor is
to its strong adsorption on the active sites, decreasing catalyst activity. adopted in this study for many reasons among them: the kinetic para-
Graaf et al. [13,30] considered a scheme of three reactions for the meters are obtained from the fluidized bed reactor experiments; sa-
three-phase methanol synthesis: the hydrogenation of CO, CO2 and the tisfactory predication and based on a strong view.
water gas shift reactions. They found that the hydrogenation of CO2 is The rate expressions for reaction (1)–(3) are given as follows:
the most important reaction. Bussche and Froment [14] considered only

Table 1
Reaction mechanisms for methanol synthesis.

Bussche & Froment [14] Lu et al. [1]

H2 (g ) + 2s ⇌ 2 H . s (1a) 2Cu2 + H2 ⇌ 2Cu2 H

(1b)

CO2 (g ) + s ⇌ O. s + CO (g ) (2a) (2b)

CO2 (g ) + O. s + s ⇌ CO3 .2s (3a)

CO3 .2s + H . s ⇌ HCO3 .2s + s (4a)

HCO3 .2s + s ⇌ HCO2 .2s + O. s (5a)

(3b)

HCO2 .2s + H . s ⇌ H2 CO2 .2s + s (6a)

H2 CO2 .2s ⇌ H2 CO. s + O. s (7a) Cu2 CH2 O + Cu2 H ⇌ Cu2 CH3 O + Cu2
(4b)

Cu2 CH3 O + Cu2 H ⇌ Cu2 CH3 OH + Cu2

H2 CO. s + H . s ⇌ H3 CO. s + s (8a) (5b)

Cu2 CH3 OH ⇌ Cu2 + CH3 OH

H3 CO. s + H . s ⇌ CH3 OH (g ) + 2s (9a) (6b)

Cu2 O + 2Cu2 H ⇌ 2Cu2 + Cu2 H2 O

O. s + H . s ⇌ OH . s + s (10a) (7b)

Cu2 H2 O ⇌ Cu2 + H2 O

OH . s + H . s ⇌ H2 O. s + s (11a) (8b)

H2 O + Cu2 ⇌ Cu2 O + H2
H2 O. s ⇌ H2 O (g ) + s (12a) (9b)

CO + Cu2 O ⇌ Cu2 + CO2

(10b)

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Table 2 Table 3
Comparison between experimental and the two-phase model prediction [1]. Hydrodynamic parameters for the bubbling fluidized bed reactor [1,32].

Pressure (MPa) Temperature (oC) 3

dp
Ar = ρg (ρp − ρg ) g (c1)
μg2
2.0 3.0 4.0 250.0 260.0 27.0 0.021
1.0 0.029 ⎛ ρg ⎞
CO conversion (%)
Experimental 28.7 40.0 48.6 30.0 40.0 45.1
εmf = 0.586 ( ) Ar
⎜ ⎟

⎝ ρp ⎠
(c2)
μg
Model 28.9 39.1 46.9 31.1 39.1 44.6 Umf = [ 25.252 + 0.0651 Ar − 25.25] (c3)
ρg dp

Gd = Umf A (c4)
k1 [PCO2 PH2 − (PCH3 OH PH2 O )/ K1 PH2 2 ] Gb = (Uo − Umf ) A (c5)
R1 = 3 dbm = 0.652[ A (Uo − Umf ) ]0.4 (c6)
[1 + K CO2 PCO2 + K CO PCO + K H2 PH2 ] (4)
dbo = 0.347(7.85 × 10−5 (Uo − Umf ))0.4 (c7)

R2 =
k2 [P H2 O − PCO2 PH2/ K2 PCO] db = dbm − (dbm − dbo) exp ( −0.3h
D )(c8)
⎡1 + K CO2 PCO2 + K CO PCO + K H2 P H2 ⎤ (5)
⎣ ⎦ Ub = Uo − Umf + 0.711(gdb )0.5 (c9)
Uo − Umf
2 2 δ= (c10)
⎛ PCH3 OH PCH3 OCH3 ⎞ Ub
R3 = k3 ⎜ − ⎟
PH2 O K3 Hmf
⎝ ⎠ (6) H= (c11)
(1 − δ )
Where: T3/2 1 1
Dij = 0.04357 2 Mi + (c12)
Mj
kmol P ⎛⎜Vi1/3 + V1/3 ⎞⎟
k1 = 35.45 exp( −1.7069 × 10 4 / R/ T ) , ⎝
j
⎠
kg s bar 2 (7) n
yj
Dim = (1 − yi )/∑ Dij
(c13)
kmol j=1
k2 = 7.3976 exp( −2.0436 × 10 4 / R/ T ) ,
kg s bar (8) j≠i
εmf Dim Ub
kmol (K cd )i = 6.78 (c17)
k3 = 8.2894 × 10 4 exp( −5.2940 × 10 4 / R/ T ) , db3
kg s bar (9)
Umf 1/2 g1/4
Dim
(K bc )i = 4.5 ⎛ ⎞ + 5.85 ⎜⎛ ⎞
⎟ (c18)
The adsorption equilibrium constants for CO2, CO and H2 are given ⎝ db ⎠
⎝ db5/4
⎠
by the following equations [1,14,27]: 1
=
1
+
1
(c19)
(Kbd)i (K cd)i (Kbc )i
K CO2 = 1.02 × 10−7 exp(6.7400 × 10 4 / R/ T ) , bar −1 (10)

K CO = 7.99 × 10−7 exp(5.8100 × 10 4 / R/ T ) , bar −1 (11) ln K1 = 4213/ T − 5.752 ln T − 1.707 × 10−3T + 2.682 × 10−6T 2
K H2 = 0.249 exp(3.4394 × 10 4 / R/ T ) , bar −1 − 7.232 × 10−10T 3 + 17.6 (13)
(12)
and the equilibrium constants K1, K2 and K3 are given by [1,27]:

Fig. 1. Schematic diagram of the multi-stage catalytic fluidized

bed reactor: (a) two beds, and (b) representation of the two-phase
model.

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Table 4
Data for the fluidized bed reactor [1].

dP 150.0 μm
D 0.026 m
Hmf 1.0 m
T 533.15 K
P 50.0 bar
Uo 0.06243 m s−1
Umf 0.02193 m s−1
ρp 1982.5 kg m−3

Fig. 4. Single bed configuration: total methanol yield as a function of catalyst 2 com-
positions for various feed compositions.

Fig. 2. Single bed configuration: total methanol yield as a function of CO2 concentration
in the feed for various catalyst compositions.

Fig. 5. Single bed configuration: actual methanol yield as a function of CO2 concentration
in the feed for various catalyst compositions.

Fig. 3. Single bed configuration: rates of reaction (1) and (2) as a function of CO2 con-
centration in the feed.

log10 K2 = 2167/ T − 0.5194 log10 T + 1.037 × 10−3T − 2.331 × 10−7T 2

− 1.2777 (14)

ln K3 = 4019/ T + 3.707 ln T − 2.783 × 10−3T + 3.8 × 10−7T 2

− 6.561 × 10 4 / T 3 − 26.64 (15)

It is worth mentioning that many investigators [1,5,31] have im-

plemented the DME production scheme of reaction (1)–(3).
Fig. 6. Single bed configuration: DME yield as a function of CO2 concentration in the feed
for various catalyst compositions.
3. Mathematical modeling
develop a new mechanism and reaction kinetics for DME synthesis
The two-phase model is well established and the most reliable
using experimental data obtained from a laboratory fluidized bed re-
model for the fluidized bed reactor. This model has been used widely
actor. Furthermore, the developed kinetics was implemented in the
used to model successfully important industrial processes such as steam
two-phase model to simulate the fluidized bed reactor based on the
reforming of methane. For the first time, Lu et al. [1] have been able to

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Fig. 7. Single bed configuration: maximum phenomena of DME yield. Fig. 10. Two-bed configuration: DME yield as a function of CO2 concentration in the feed
for various catalyst compositions.

Fig. 8. Single bed configuration: DME selectivity as a function of CO2 concentration in the
feed for various catalyst compositions.
Fig. 11. Two-bed configuration: DME selectivity as a function of CO2 concentration in the
feed for various catalyst compositions.

Fig. 9. Two-bed configuration: actual methanol yield as a function of CO2 concentration

in the feed for various catalyst compositions.
Fig. 12. Two-bed configuration: DME yield maximum phenomena.

assumption that the dense phase is fully back-mixed (P-M model).

Table 2 shows the prediction accuracy of the model compared to ex- numerical simulation of the multi-stage fluidized bed reactor.
perimental results as reported by Lu et al. [1] at SV = 3000 ml/gcat/h Unfortunately there is not yet experimental data available for this new
and H2/CO = 1.0. The experimental data estimated from the points on novel configuration as a basis for the comparison. A schematic diagram
the plots provided by Lu et al. [1]. of the two-bed freely bubbling fluidized bed reactor is shown in
In this study the reliable two-phase model is implemented for the Fig. 1(a). Also, a schematic representation of the bubble and dense

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and θ1 and θ2 are the mass fraction of catalyst 1 and 2, respectively.

Defining the dimensionless rate of reaction as:
R′ = ρP (1 − εmf )(1 − δ ) AH R/ Cref Gd (22)
Substituting Eq. (20) into the dimensionless form of Eq. (21), we
obtain:
2
(YiF − Yid ) + βi (Yib − Yid ) + θ1 ∑ γij R′ j+θ2 γi3 R′3 = 0 , i = 1,...,6
j=1

(23)
Total methanol and actual methanol yield are defined by the fol-
lowing relations [1,5,27]:
Total methanol formed
Total methanol yield (%) = Total carbon in
× 100
Methanol output + Methanol converted to DME FCH3 OH + 2FCH3 OCH3
= × 100 = × 100
(FCO2 + FCO )in (FCO2 + FCO )in

Fig. 13. Two-bed configuration: DME selectivity maximum phenomena. (24)

Methanol output
Actual methanol yield (%) = × 100
phases of the two-phase model are depicted in Fig. 1(b). The model Total carbon in
equations are derived based on the following main assumptions: an FCH3 OH
== × 100
isothermal steady state operation, the bubbling bed is composed of the (FCO2 + FCO )in (25)
dense and bubble phases, the bubble phase in plug flow, the bubbles are
and DME yield and selectivity are defined as:
spherical, the dense phase is well mixed, ideal gas behavior, there is no
catalyst deactivation, and the intraparticle diffusion resistance is ne- Methanol converted to DME
DME yield (%) = × 100
glected due to the small size of the catalyst particle. total carbon in
2FCH3 OCH3
= × 100
3.1. Conservation equations for the bubble phase (FCO2 + FCO )in (26)

DME reaction scheme involves 6-components: CO2, H2, CH3OH, Methanol converted to DME
DME selectivity (%) = × 100
H2O, CO, and CH3OCH3. A differential molar balance on the ith com- total methanol formed
ponent in the bubble phase gives: 2FCH3 OCH3
= × 100
FCH3 OH + 2FCH3 OCH3 (27)
dCib (K ) A (C − Cid )
= − bd i b ib , i = 1,...,6
dh Gb (16) The set on of non-linear algebraic Eq. (23) are solved by an IMSL
subroutine called ZSPOW. The Golden search method is used to cal-
With the initial conditions:
culate the locus of the maxima
Cib (0) = Cid (0) = CiF (17)
4. Results and discussion
where the subscript b and d refer to bubble and dense phases, respec-
tively.
The hydrodynamic parameters of the bubbling fluidized reactor are
Defining the following dimensionless state variables and para-
given in Table 3 [1,32], and the data used for the simulation are given
meters:
in Table 4 [1]. The content of CO2 and CO in the feed is an important
Yib = Cib/ Cref , Yid = Cid/ Cref , Yif = CiF / Cr ef , factor for the production of DME because these components are the
Z = h/H , αi = (Kbd )i Ab H / Gb, βi = (Kbd )i Ab H / Gd (18) carbon sources for the reactions and also used to characterize the feed.
We utilized the content of these components in the feed as a key
And, the average dimensionless concentration of component i in the parameter. In this study, we implemented the concentration range of
bubble phase: Cox in the feed [CO2 + CO = 0–25 mol%] used by several investigators
H 1 [3,14,29,31]. Also, we denote the methanol synthesis and dehydration
Yib = ∫ Yib dh/H = ∫ Yib dZ catalysts as catalyst 1 and 2, respectively. Different bed configurations
0 0 (19) are considered and all beds have the same amount of catalyst and the
total amount of the catalyst is kept constant to ensure fair comparison.
Hence, Eq. (16) gives:
Yib = Yid + (YiF − Yid )[1 − exp(−αi )]/ αi (20) 4.1. Single-bed reactor configuration

The fundamental understanding of the single-bed configuration is

3.2. Conservation equations for the dense phase
essential for the study of the two-bed configuration because this stage
feeds the second stage. Here, we considered various catalyst composi-
The molar balance on the ith component in the dense phase gives:
tions to evaluate the performance of the fluidized bed reactor. A lim-
H
Gd Cid = Gd CiF + ∫0 (Kbd )i Ab (Cib − Cid ) dh+ iting case of catalyst 1 alone [A(θ1 = 100%, θ2 = 0%)] is considered to
represent methanol production by methanol synthesis reactions. In
2
⎡ ⎤ addition to three bifunctional catalyst
ρP (1 − εmf )(1 − δ ) AH ⎢θ1 ∑ γij Rj + θ2 γi3 R3⎥ , i = 1,...,6
compositions as follows: a bifunctional catalyst rich in catalyst 1
⎣ j=1 ⎦ (21)
and lean in catalyst 2 [B (θ1 = 80%, θ2 = 20%)], a bifunctional cata-
where γij is the stoichiometric coefficient of component i in the jth re- lyst with equal catalysts loading [C (θ1 = 50%, θ2 = 50%)], a bifunc-
action (positive for products, negative for reactants and zero for inerts) tional catalyst lean in catalyst 1 and rich in catalyst 2 [D (θ1 = 20%,

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θ2 = 80%)]. Beside another limiting case of catalyst 2 alone [E compositions, the DME yield decreases as CO2 concentration in the feed
(θ1 = 0%, θ2 = 100%)]. This limiting case of methanol dehydration is increased. It is interesting to note that at a specific feed composition
has no practical meaning for DME production in the single-bed con- the DME yield increases and decreases as the dehydration catalyst
figuration, since the methanol dehydration reaction cannot occur loading is increased leading to the appearance of the maximum phe-
without methanol, but can be considered as a frame of reference. The nomenon. This maximum phenomenon is exemplified by two feed
total methanol yield produced by these catalyst configurations as a compositions as shown in Fig. 7. The maxima are formed due to the fact
function of CO2 concentration in the feed is depicted in Fig. 2. As it can that the increase of catalyst 2 loading will be at the expense of catalyst 1
be seen that for a feed with low CO2 concentration, a significant in- loading. The locus of maxima is presented for the whole range of the
crease of the total methanol yield is obtained by implementing the bi- feed compositions. The corresponding DME selectivity is presented in
functional catalyst compared to only methanol synthesis process, Fig. 8. As it can be seen that the DME selectivity is favored at a high CO
A(100%, 0%). The total methanol yield decreases steadily as CO2 concentration in the feed and the bifunctional catalyst is rich in the
content in the feed is increased. It is interesting to note that two types of methanol dehydration catalyst because at these conditions the water-
maxima phenomena can be identified. The first maximum point is gas shift reaction has a strong positive effective impact on the reaction
clearly shown in the profile of the limiting case A(100%, 0%). This synergy.
maximum point has been developed as the total methanol yield varies
with CO2 concentration in the feed. The maximum point appears due to 4.2. Two-bed configuration
the increase and decrease of rate of reactions as demonstrated by Fig. 3.
The rate of reactions The fluidized bed reactor with two-bed configuration has a very
increase and decrease owing to conflicting effects of positive and large possible number of permutations of the bifunctional catalyst
negative synergic coupled with water inhibition effect. According to the loadings. In this study, the first bed composition is kept constant at an
Le Châtelier's principle of equilibrium, reaction (1) and (2) are re- optimum value of (θ11 = 52%, θ21 = 48%) obtained from the results of
versible with a strong synergy between them. The positive synergetic the above single bed investigation while the second bed composition is
effect promotes kinetically and thermodynamically reaction (1) and (2) varied. The same three bifunctional catalyst compositions used in the
in order to improve the total methanol yield as follows: water formed single bed are utilized in the study of the second bed as follows: a bi-
by reaction (1) is consumed by reaction (2), and H2 and CO2 produced functional catalyst rich in the methanol synthesis catalyst (80%, 20%),
by reaction (2) favor reaction (1). The negative synergic effect becomes an equal loading bifunctional catalyst composition (50%, 50%), a bi-
significant when the prevailing reaction conditions favor backward functional catalyst rich in the methanol dehydration catalyst (20%,
rates, causing excessive water formation and decreasing the rate of 80%). Fig. 9 shows the influence of the bifunctional
reactions. It is clearly shown in Fig. 3 that the increase of CO2 in the catalyst composition in bed2 on the actual methanol yield as a
feed has a more pronounced effect on the water-gas shift reaction (2), function of CO2 concentration in the feed. The results clearly show that
and the reaction is completely reversed after the equilibrium point (EP). the second bed exhibits the maximum phenomenon in a similar way to
This maximum phenomenon type was also observed by Ng et al. [5] in the first bed. It is once more revealed that the role of the strong sy-
an internal recycle reactor. The second maximum phenomenon is not nergistic effect between the reactions is responsible for the maxima
clearly observed in Fig. 2. As it can be seen in Fig. 2 that, the total formation as explained earlier. However, the maxima are shifted to the
methanol yield increases and decreases by increasing the methanol right in the second bed case. The corresponding DME yield and se-
dehydration catalyst (catalyst 2) load in the bifunctional catalyst lectivity obtained from the second bed are presented in Figs. 10 and 11,
composition. The maximum is principally formed when the methanol respectively. It is evident that the addition of the second bed (bed2)
dehydration catalyst (catalyst 2) increases at the expense of the me- gives a substantial increase
thanol synthesis catalyst (catalyst 1). In fact the formation of this of the DME yield compared to the first bed (bed1) and in particular
maximum is more complex than the first case because the composition for CO rich feeds. About 32.67% increase in DME yield is achieved by
of the bifunctional catalyst and the methanol dehydration reaction (3) the second bed (bed2) at a feed concentration of [CO2/(CO2 + CO)
become additional effective dimensions on the synergy between the = 0.01] and a catalyst composition of (50%,50%). This improvement is
reactions. Two examples of the effect of the feed composition on the achieved owing to the fact that the second bed has different feed and
total methanol yield as a function of bifunctional catalyst composition bed composition compared to the first bed and single bed configuration.
are depicted in Fig. 4. The maxima are clearly shown and their values It is seen that the enhancement of the DME yield decreases steadily with
decrease with the increase of CO2 content in the feed. To follow this the increase of CO2 concentration in the feed attributed to the in-
behavior for a wide range of the feed composition, the locus of the creasing of the water inhibition effect. Also, a significant enhancement
maxima is also shown as a dotted line. It is interesting that the maxima of the DME selectivity is achieved by the second bed (bed2). Almost
are confined to a small range of bifunctional catalyst composition, 100% DME selectivity is obtained at a feed of low CO2 concentration
θ2 = 48.5%–50.4%. and bed composition of (50%, 50%). The DME yield and selectivity are
In Fig. 5 is shown the influence of the bifunctional catalyst com- favored at a low CO2 concentration in the feed owing to the effective
position on the actual methanol yield as a function of the feed com- positive synergy as discussed earlier. It is interesting to observe that at a
position. The results indicate that for a specific reactor feed con- specific feed composition the DME yield and selectivity increases and
centration the actual methanol yield decreases as the concentration of decreases as the concentration of the catalyst 2 increases in the com-
the methanol synthesis catalyst (catalyst 1) decreases in the bifunc- position of the bifunctional catalyst. This behavior leads to the ap-
tional catalyst composition. As one can see, for a certain catalyst bed pearance of the maxima phenomena of the DME yield and selectivity as
composition that the actual methanol yield profiles assume maximum shown in Figs. 12 and 13, respectively. The reasons for the formation of
values with the increase of CO2 concentration in the feed. This max- such maxima have been offered in details earlier.
imum is formed as a balance between the rates of methanol produced
by reaction (1) and consumed by reaction (3). The locus of maxima 5. Conclusions
shows that, the locations of the maxima are shifted to the right as the
concentration of catalyst 1 decreases and CO2 concentration in the feed A mathematical model has been utilized to explore the potential
increases. This shift can be thought of as impact of compensation of CO2 application of a multi-stage fluidized bed catalytic reactor for efficient
concentration on reaction (1) due to the decrease of catalyst 1. production of DME. The simulation results indicated that the two-bed
Fig. 6 shows DME yield versus CO2 content in the feed for various configuration gives a substantial enhancement of DME yield (32.67%)
bifunctional catalyst compositions. For all bifunctional catalyst compared to the yield from the single-bed. Also, DME selectivity of

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M.E.E. Abashar Chemical Engineering & Processing: Process Intensification 122 (2017) 172–180

almost 100% is obtained. This significant improvement achieved, be- http://dx.doi.org/10.1016/j.cej.2013.08.062.

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