Chemical Engineering Science 59 (2004) 5455 – 5464

www.elsevier.com/locate/ces

Simulation and experiment study of dimethyl ether synthesis from syngas

in a fluidized-bed reactor
Wen-Zhi Lu, Li-Hua Teng, Wen-De Xiao∗
Department of Chemical Engineering, UNILAB Research Center of Chemical Reaction Engineering, East China University of Science and Technology,
130 Mei Long Road, Shanghai 200237, China

Received 2 March 2004

Available online 28 August 2004

Abstract
As syngas to dimethyl ether (DME) reaction is highly exothermic and the catalyst temperature window is very narrow, fluidized-bed
reactor is an ideal candidate as it is highly effective both in heat and mass transfer. In this paper, a new mechanism and kinetics model
for DME synthesis are established and a laboratory fluidized-bed reactor is set up. Experiments are carried out to assess the performance
of DME synthesis in this reactor. The experimental results show that CO conversion and DME productivity are higher than those of fixed
bed or slurry reactor. Two two-phase models are used to simulate DME synthesis in the lab fluidized-bed reactor with the bubble phase
assumed to be in plug flow, and the dense phase in plug flow (P–P model) and in fully back-mixed flow (P–M model). Comparison
between calculated and experimental results shows P–M is more valid than P–P model, and then influences of different parameters on
reactor performance are investigated based on P–M model.
䉷 2004 Elsevier Ltd. All rights reserved.

Keywords: Dimethyl ether; Fluidized-bed reactor; Syngas; Simulation; Kinetics model

1. Introduction
Dimethyl ether (DME), as a multi-source, multi-purpose
product, has received growing attention considering global
environment pollution and energy supply problem today.
DME can be produced from syngas, which is from natu-
ral gas, coal or biomass. DME has wide applications, such
as LPG substitute, transportation fuel, propellant, chemical
feedstock and fuel cell fuel (Ng et al., 1999).
Been identified as a potential diesel and cooking fuel,
DME has many excellent characteristics. It has an oxygen
concentration of 34.78% and can be burned without soot
emission, while for traditional diesel fuels, one cannot expect
simultaneous NOx and soot emission control target. It has a
boiling point of −25 ◦ C, which is 20 ◦ C higher than LPG and
can be liquidized at 0.54 MPa (20 ◦ C). Therefore, based on
the matured technology of LPG application, there does not
exist any problem for the storage, transportation and usage
of DME.
At present, DME is commercially prepared by dehydra-
tion of methanol using acidic porous catalysts such as zeo-
lites, silica–alumina, alumina, etc. It has been reported that
using syngas as a starting material, DME can be prepared in
a one-step process, which is more thermodynamically and
economically favorable than the two-step process of syngas
to methanol and further to DME.
Three reactions take place in the syngas-to-DME process,
namely,
Methanol synthesis reaction
CO2 + 3H2 ⇔ CH3 OH + H2 O

H = −56.33 kJ/mol (1)
Methanol dehydration reaction

∗ Corresponding author. Tel./fax: +86-21-64252814.

2CH3 OH ⇔ CH3 OCH3 + H2 O
E-mail address: wdxiao@ecust.edu.cn (W.-D. Xiao).
H = −21.255 kJ/mol (2)

0009-2509/$ - see front matter 䉷 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.07.031
5456 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464
Water gas shift reaction
CO + H2 O ⇔ H2 + CO2

H = −40.9 kJ/mol (3)
Overall reaction
3CO + 3H2 ⇔ CH3 OCH3 + CO2

H = −256.615 kJ/mol (4)
Reactions (1) and (3) are catalyzed by a methanol synthe-
sis catalyst (Cu/ZnO/Al2 O3 ) and Reaction (2) by an acidic
catalyst (e.g. HZSM-5). These three reactions form a syn-
ergistic system yielding higher syngas conversion or greater
productivity when compared to the syngas-to-methanol pro-
cess. The synergy works in the following manner: methanol,
which would otherwise be near its equilibrium value, is con-
sumed by Reaction (2), and water formed by Reactions (2)
and (1) is consumed by Reaction (3), while Reaction (3)
generates hydrogen which improves Reaction (1).
All the three reactions are reversible and exothermic.
Moreover, the catalyst for Reactions (1) and (3) is subject
to severe deactivation when overheated to above 270 ◦ C. To
avoid thermodynamic limitations and excessive catalyst de-
activation, conventional gas-phase reactors must be operated
at a low per-pass conversion to maintain reactor temperature
below 270 ◦ C, implementing a high-syngas recycle rate, and
resulting in large capital investments and operating costs. In
addition, in order to avoid serious pressure drop, the diam-
eter of catalyst particles in fixed-bed reactor is usually over
4 mm, which brings a certain inner mass-transfer resistance.
Manufacture of DME in one step in slurry reactor was
proposed by Air Product and Chemicals, Inc. (Brown et al.,
1991). This kind of reactor can provide not only an efficient
heat management, but also a very high mass-transfer resis-
tance, as an extra liquid phase is added. This is demonstrated
by the experimental results reported by Du et al. (1993)
and Guo et al. (2000), where the apparent activity energies
of methanol synthesis by CO hydrogenation and methanol
dehydration reactions have been determined as 102.4 and
99.8 kJ/mol in a gas-phase fixed-bed reactor, and as 14.1
and 23.5 kJ/mol in a slurry reactor, respectively, thus im-
plying a considerable inter-phase mass-transfer resistance.
The fluidized-bed reactor is proposed as an ideal reactor
for the DME synthesis (Xiao and Lu, 2002). Compared with
the slurry reactor and fixed-bed reactor, the gas–solid mass-
transfer resistance in a fluidized-bed reactor is so small that
it can be neglected, and excellent temperature control is also
achievable due to the vigorous mixing of catalyst particles
in the bed. Simulation of fluidized-bed reactor for DME
synthesis has been performed by Lu et al. (2003) using P–P
model, which shows the great advantage of fluidized-bed
over fixed-bed or slurry reactor.
In this paper, a laboratory fluidized-bed reactor, 0.026 m
in diameter and 2 m high, is established. Experiments are
carried out to assess the performance of DME synthesis in
the fluidized-bed reactor, and results show that CO conver-
sion and DME productivity are better compared with those
100
o
90 250 C
o
80 260 C
o
70 270 C
60
XCO(%)
50
40
30
20
10
0
4 5 6
Cu-ZnO-Al2O3 : HZSM-5(wt)
Fig. 1. Activity of Cu–ZnO–Al2 O3 /HZSM-5 catalyst P = 3 MPa,
H2 /CO = 1, SV = 3000 ml/g/h.
in a fixed bed or slurry reactor. Then a two-phase model is
used to simulate DME synthesis in a fluidized-bed reactor,
and simulation results are compared with those from exper-
iments. Finally, the influences of different factors, such as
pressure, temperature, H2 /CO ratio in feed gas and space
velocity are simulated and analyzed.
2. Catalyst and kinetics
The selected catalyst is Cu–ZnO–Al2 O3 /HZSM-5, man-
ufactured by co-precipitation deposition method with the
component for methanol synthesis, Cu–ZnO–Al2 O3 , and
that for methanol dehydration, HZSM-5. Fig. 1 shows the
activity of Cu–ZnO–Al2 O3 /HZSM-5 at different tempera-
tures in a lab fixed-bed reactor. The optimum ratio of the
two components is about 5.0 for Cu–ZnO–Al2 O3 /HZSM-5
catalyst.
According to the recent analytical results by XPS and
XAES method (Li, 2004), the main active center for
methanol synthesis on this catalyst is Cu(0), which was
proposed to be Cu clusters (Nakatsuji and Hu, 2000),
but not Cu atom. The key intermediate of the methanol
synthesis, which is formed from the CO2 and Cu–Cu clus-
ters, is supposed to be the ring-type ester. This kind of
ester also has the structure of two C–O bonds observed
by others (Neophytides et al., 1992), and can be hydro-
genated more easily than formate species, although formate
is usually assumed to be the key intermediate (Bussche
and Froment, 1996). Water gas shift reaction also takes
place on Cu clusters and it proceeds through two steps:
H2 O dehydrogenation to provide adsorbed O and CO2
formed by the quick reaction of CO with adsorbed O (Sun
et al., 1998). Thus the reaction mechanisms for CO2 hy-
drogenation to methanol and water gas shift reaction are as
 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464 5457

follows: Assuming reaction (m) to be the rate-determining step,

the expression of rate of methanol dehydration reaction is
2Cu2 + H2 
 2Cu2 H, (a) as follows:
O C O (PM
2 /P ) − (P /K
W D P ,2 )
r 2 = K2 . (7)
CO2 + Cu2 
 Cu Cu, (b) (1 + KM PM + KH2 O PW )2
O C O The experimental results showed that, both methanol and
Cu Cu + 2Cu2 H 
 Cu2 CH2 O + Cu2 O + Cu2 , (c) water had very little concentration in the outlet mixture. and
the syngas to DME reaction proceeds through the overall
Cu2 CH2 O + Cu2 H 
 Cu2 CH3 O + Cu2 , (d) reaction: 3CO + 3H2 = DME + CO2 . Thus the terms of
methanol and water adsorption can be neglected and the
Cu2 CH3 O + Cu2 H 
 Cu2 CH3 OH + Cu2 , (e) above-kinetics equations can be simplified as follows:
Cu2 CH3 OH 
 Cu2 + CH3 OH(a), (f) PCO2 PH2 (1 − PW PM /KP ,1 PCO2 PH32 )
r1 = K1
, (8)
Cu2 O + 2Cu2 H 
 2Cu2 + Cu2 H2 O, (g) (1 + KCO2 PCO2 + KCO PCO + KH2 PH2 )3
 
Cu2 H2 O 
 Cu2 + H2 O(a), (h) PM2
PD
r2 = K2 − , (9)
PW KP ,2
H2 O(a) + Cu2 
 Cu2 O + H2 , (i)
PW − PCO2 PH2 /KP ,3 PCO
CO + Cu2 O 
 Cu2 + CO2 . (j) r 3 = K3
. (10)
1 + KCO2 PCO2 + KCO PCO + KH2 PH2
Reaction (c) and (i) are assumed to be the rate determin-
ing steps individually, and thus expressions of the rate of Finally, the kinetic parameters in the above expressions
methanol synthesis and water gas shift reaction are obtained are obtained by regression of the experimental data, which
as follows:
PCO2 PH2 (1 − PW PM /KP ,1 PCO2 PH32 )
r1 = K1
(5)
(1 + KCO2 PCO2 + KCO PCO + KMEO PM + KW PW + KH2 PH2 )3

PW − PCO2 PH2 /KP ,3 PCO

r3 = K3
(6)
1 + KCO2 PCO2 + KCO PCO + KM PM + KW PW + KH2 PH2

Methanol formed by CO2 hydrogenation is transferred to

acidic site on HZSM-5 where it obtains a proton. Accord- are as follows:
ing to organic chemistry theory, it forms a leaving radical
of H2 O, and produces a carbon cation. DME is then formed K1 = 35.45 exp(−1.7069 × 104 /R/T ), (11)
by a nucleophilic-displacement reaction caused by another
K2 = 8.2894 × 104 exp(−5.2940 × 104 /R/T ), (12)
adsorbed methanol molecule on the carbon cation. This re-
action mechanism is as follows: K3 = 7.3976 exp(−2.0436 × 104 /R/T ), (13)
CH3 OH(a) + HX 
 HXCH3 OH, (k) where the adsorption constants, KH2 , KCO2 , and KCO are
+ − given by Bussche and Froment (1996) and Herman and Klier
HXCH3 OH 
 CH3 X + H2 O(a), (l)
(1979), shown in the following:
CH3+
KH2 = 0.249 exp(3.4394 × 104 /R/T ), (14)
+ − -
CH3 X + HXCH3 OH 
 HXCH3 O H + X , (m)
KCO2 = 1.02 × 10−7 exp(6.7400 × 104 /R/T ), (15)
+ CH3
CH3
KCO = 7.99 × 10−7 exp(5.8100 × 104 /R/T ) (16)
HXCH3 O H HXCH3 O H+, (n)
and the equilibrium constants for the three reactions are
CH3 given by Zhang et al. (2001) and Herman et al. (1979), shown
HXCH3 O H+  HXCH3 − O − CH3 + H+ ,
 (o) as
ln KP ,1 =4213/T − 5.752 ln T − 1.707 × 10−3 T
HXCH3 − O − CH3 
 CH3 OCH3 + HX, (p)
+2.682 × 10−6 T 2 − 7.232 × 10−10 T 3 + 17.6,
H+ + X− 
 HX. (q) (17)
5458 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464

FIC 4. Model development

Filter
The two-phase model, representing the bubble phase and
H2
the surrounding dense phase, has proved to be the most suit-
FIC able model for the fluidized-bed reactor modeling (Werther,
1980), and the details of this model can be found in Kunii
PIC
CO
et al. (1991) with the hydrodynamic and transport property
To
correlations listed in Table 1. It postulates that the gas in
FIC vent excess of that necessary for the catalyst particles to fluidize
passes through the bed in the form of bubbles.
CO2 GC
The assumption of plug flow in the bubble phase is usu-
ally valid, but it becomes very doubtful whether the dense
TC1-
phase should be modeled as being fully back-mixed (P–M
FIC 4 model) or in plug flow (P–P model). Wagialla et al. (1991)
To
vent adopted P–M model for the simulation of methanol synthe-
N2
sis, but Fernandes and Lona (2001) adopted P–P model for
the simulation of polyethylene production.
Fig. 2. Schematic view of the fluidized-bed reactor system. Kunii and Levenspiel (1969, 1991) conclude that the in-
crease of the ratio of bed height-to-diameter (Lf /dt ), espe-
ln KP ,2 =4019/T + 3.707 ln T − 2.783 × 10−3 T cially over 10, leads to plug flow in dense phase, and that
there is also a general principle to judge the flow type in
+3.8 × 10−7 T 2 − 6.561 × 104 /T 3 − 26.64,
dense phase: if u0 /umf > 3–11, the reverse flow of gas in
(18) dense phase may happen, because the increase of gas ve-
locity leads to more back-mixing of solid particles in dense
log KP ,3 =2167/T − 0.5194 log T + 1.037 × 10−3 T phase. In this paper, u0 /umf is between 2 and 8 under typical
−2.331 × 10−7 T 2 − 1.2777. (19) conditions, and the ratio of bed height to diameter (Lf /dt )
equals to about 40. Thus it seems that the assumption of
flow type in dense phase should be determined by the com-
3. Experimental parison of simulation with experimental results.

The experimental setup scheme is shown in Fig. 2. In the 4.1. Assumptions

feed section, the reactants CO, CO2 , and H2 and the sweep-
ing gas N2 are led through a set of mass flow controllers. The model employs the following assumptions:
The stainless-steel reactor is of the tubular type, with an
internal diameter of 0.026 m and a length of 2 m, withstand- (i) The bubble phase does not contain solids and is in plug
ing temperatures up to 400 ◦ C and pressures of 100 bar, gov- flow. The extent of reaction in the bubble-cloud phase
erned by a membrane back pressure controller. In the upper is negligible.
of the reactor, there is an expanding section, with the diam- (ii) The dense phase is assumed to be in plug flow or be
eter of 0.1 m, which decreases the gas velocity and the loss fully back-mixed, and the temperature in dense phase
of fine catalyst particles. Above the reactor, a filter is also keeps constant.
fitted to capture the fine catalysts in the outlet gas. The reac- (iii) The ideal gas law applies to the gas-phase in both
tor is divided into two heating zones, each with its own PID phases.
temperature controller, facilitating isothermal operation. The (iv) The mass and heat-transfer resistances between the par-
temperature profile along the bed is measured by means of ticles and the dense-phase gas are negligible.
four thermocouples (TC), from the inlet to the outlet of the
reactor. 4.2. Mass balance on bubble and dense phases
The catalyst involved, with the mean diameter of 150 m,
is positioned in the reactor on the distribution board having Having assumed uniform temperature in dense phase, we
an orifice ratio of 1%. The height of the packed bed at typical only have to consider the material balance equations for
conditions amounts to about 1 m. component i in both phases and energy balance in bubble
The high-pressure effluent pipelines, are constantly kept phase, which are as follows:
at temperatures over 100 ◦ C, to avoid possible condensation The steady state mass balance for the ith component in
of water or methanol, though their concentrations are very the bubble phase is given by
small after the reactions. The gas finally reaches the analysis  
dNib Nid Nib
section, where a gas chromatograph determines its compo- Bubble phase : = (Kbd )ib − A
. (20)
sition. dz Qd Qb
 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464 5459

Table 1
Hydrodynamic and transport property correlations
 0.029   0.021
f
Bed voidage at minimum fluidization mf = 0.586 1.0
Ar  ,
p
where
dp3
Ar = f (p − f ) g —
2
f
f


Superficialvelocity at minimum fluidization umf = f dp
25.252 + 0.0651Ar − 25.25
Bubble diameter dB = dBM − (dBM − dBO ) exp −0.3zdt
where 
0.4
dBM = 0.652 A u0 − umf ,

0.4
dBo = 0.347 An u0 − umf ,
An = 7.85 × 10−5
Bubble rising velocity ub = u0 − umf + 0.711(gd B )0.5
Volume fraction of bubble phase to overall bed
= Qb /ub /A
Dense-phase volumetric flow rate Qd = umf A
Bubble-phase volumetric flow rate Qb = (u0 − umf )A0
Expanded bed height H = Hmf /(1 −
)
1 1 1
(Kbd )ib = (Kbc )ib + (Kcd )ib , 
u  1/2
Dim g 1/4
mf
(Kbc )ib = 4.5 dB + 5.85 5/4 ,
Overall mass-transfer coefficient (bubble phase–dense phase) based on bubble volume dB
 1/2
mf Dim ub
(Kcd )ib = 6.78 3
dB

1−xi
Diffusivity of component i in gas mixture Dim = n
(x /D )
j = 1 j ij
j = i
Dij = 0.04357 T 3/2 1 1
Binary diffusivity 1/3
P (Vi
1/3
+Vj )2 Mi + M j

1 1 1
(Hbd )b = (Hbc )b + (Hcd )b ,
 1/2
u  kg g g 1/2 Cpg
mf g Cpg
Overallheat-transfer coefficient (bubble-dense phase) based on bubble volume (Hbc )b = 4.5 dB + 5.85 5/2 ,
dB
k 
g g Cpg mf ubr 1/2
(Hcd )b = 6.78 dB

The mass balance for the ith component in the dense phase Rearranging Eq. (7) and integrating (noting that Nib =
is given by (Nib )in at z = 0) we obtain:
Dense phase (plug flow):
   
  Nid Nib (Nib )in Nid
dNid Nid Nib − =− − e−ai z , (23)
=−(Kbd )ib − A
+ p (1 − mf )(1 −
) Qd Qb Qb Qd
dz Qd Qb

3
where
× ij rj . (21)
j =1
(Kbd )ib
i = , (24)
Dense phase (fully back-mixed flow): ub
 H  
Nid Nib since
Nid =(Nid )in − (Kbd )ib − A
dz
0 Qd Qb
3 (Nib )in (Ni )in
= (25)
+AH (1 − mf )(1 −
)p ij rj , (22) Qb uin A
j =1
then
where ij refers to stoichiometric coefficient of component
i in reaction j (negative for reactants, positive for products    
Nid Nib (Ni )in Nid
and zero for components not appearing in reaction), and rj − =− − e−ai z . (26)
Qd Qb uin A Qd
refers to kinetic rate of reaction j .
5460 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464

Table 2 5. Results and discussions

Reactor operating conditions for the base case

Operating conditions Data 5.1. Comparison of different reactors

Reactor diameter 0.026 m
Bed height at minimum fluidization 1.0 m The industrial implementation of the syngas-to-DME pro-
Expanded bed height 1.0 m cess for fuel production requires a large-scale, and is gen-
Catalyst density 1982.5 kg/m3
Voidage of the dense phase 0.428
erally based on the coal-gasified syngas, so-called the CO-
Catalyst particle diameter 150 m rich synthesis gas. The syngas-to-DME process is highly
Reactor temperature 533.15 K exothermic, as can be seen from Eq. (4). Thus, the critical
Superficial gas velocity at minimum fluidization 0.02193 m/s factor for DME reactor design is the management of the heat
Feed gas velocity 0.06243 m/s released by reactions. It can be estimated that the heat re-
leased by DME production can produce 2.4 tons steam per
ton of DME, equivalent to an adiabatic temperature rise of
about 1000 ◦ C at a complete conversion of syngas with a 1:1
ratio of H2 : CO. This problem is especially significant as the
Substituting Eq. (26) into Eq. (22) and integrating we catalyst of methanol synthesis may be deactivated rapidly
obtain: when the temperature is over 270 ◦ C and the active temper-
  ature window is from 230 to 270 ◦ C.
(Ni )in Nid  
Nid =(Nid )in + Qb − 1 − e−ai H In this section, three kinds of reactors have been consid-
uin A Qd ered for comparing the performance of the syngas-to-DME
3 process: a fixed-bed, a fluidized bed, and a slurry reactor. The
+AH (1 − mf )(1 −
)p ij rj . (27) fixed bed reactor is the type of wall-cooled shell-and-tubes,
j =1 and the steam is co-produced in the shell side, which means
the heat removal rate is defined by the inside of the tube.
At z=0, Nib = (Ni )in ∗ Qb /(Qb + Qd ), According to Lu et al. (2002), for a CO-rich syngas with a
Nid = (Ni )in ∗ Qd /(Qb + Qd ). (28) H2 /CO ratio of 1, the space velocity of a fixed-bed reactor
should be greater than 15, 000 ml/gcat/h to maintain the re-
Energy balance equations:
actor temperature below 270 ◦ C at 4 MPa, the upper limit of
dTb the operating temperature range of the methanol synthesis
Bubble phase : = (Hbd )b (Td − Tb )/(g Cpg ub ). (29) catalyst. This situation produces a very limited syngas con-
dz
version, about 10%, and requires a high-syngas recycling
The P–P model equations can be solved by the ratio (up to 10), inevitably resulting in a high energy con-
Runge–Kutta method. In comparison, the solution of P–M sumption and a low productivity. A conclusion drawn by Lu
model equations is more complicated. Eq. (27) constitutes et al. (2002) is that the fixed-bed reactor is more suitable for
a system of six simultaneous nonlinear algebraic equations the H2 -rich synthesis gas.
and the Newton–Raphson numerical technique is used for The slurry reactor, such as that used in LPDME pro-
solving this set of equations. First, the value of reactor cess developed by Air Products and Chemicals, Inc. (Brown
outlet gas velocity is assumed, and thus the mean volume et al., 1991), can provide an excellent heat management,
fraction of bubble phase to overall bed and expanded bed since the slurry phase (liquid medium + fine catalyst parti-
height are obtained, then Eq. (27) can be solved and the cles) possesses a heat capacity 1000 times larger than the gas
molecule number of each component in dense phase (Nid ) phase, with an adiabatic temperature rise of the reacting flow
can be obtained. By substitution Nid into Eq. (20) and in- less than 20 ◦ C, and it can be operated adiabatically with
tegration, the reactor outlet gas velocity is obtained, and if an outside recycle flow for heat removal. Nevertheless, the
it is consistent with the previous assumed value, the calcu- added liquid medium, generally consisting of paraffin wax,
lated results can be supposed to be the right solution, or else adds two mass-transfer resistances through the gas–liquid
further assumption of outlet gas velocity value is required. and the liquid–solid interfaces, which cause a constraint to
CO conversion (XCO ) and DME selectivity in organic the productivity. Wang et al. (2001) published the experi-
products (SDME ) are defined as follows: mental results obtained in a laboratory slurry reactor. It was
reported that the CO conversion was about 17%, the selec-
(NCO )in − (NCO )out tivity of DME was 70% (30% of methanol), and the DME
XCO =
(NCO )in productivity resulted to be 0.2 g/gcat/h, at the conditions:
2NDME T = 260 ◦ C, P = 4.0 MPa, H2 /CO = 1.0, and gas space ve-
SDME = locity of 3000 ml/gcat/h.
2NDME + NMEOH
Under the same conditions as the slurry reactor as reported
Reactor operating conditions for the base case are listed by Wang et al. (2001), however, the experimental results in
in Tables 2–3. this work show that CO conversion and DME selectivity can
 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464 5461

Table 3
Comparison of different reactor performance for DME synthesis

Fluidized bed Slurry reactor ( Wang et al., 2001) Fixed bed ( Lu et al., 2002)
CO conversion (XCO ) 48.5% 17% 10.7%
DME selectivity (SDME ) 97% 70% 91.9%
DME productivity (PDME ) 0.49 g/g/h 0.2 g/g/h 0.5 g/g/h
Space velocity (SV ) 3000 ml/g/h 3000 ml/g/h 15, 000 ml/g/h

100 100
90 Experiment 90 Experiment
P-P model P-P model
80 80
P-M model P-M model
70 70
60 60
XCO(%)

XCO(%)
50 50
40 40
30 30
20 20
10 10
0 0
0.5 1.0 1.5 2.0 2.5 1 2 3 4 5
H2 /CO P(MPa)

Fig. 3. Effect of feed composition on simulation and experiment results: Fig. 4. Effect of pressure on simulation and experiment results:
P = 3 MPa, T = 260 ◦ C, SV = 3000 ml/gcat/h. H2 /CO = 1, T = 260 ◦ C, SV = 3000 ml/gcat/h.

100
90 Experiment
be as high as up to 48.5% and 97.0%, respectively, with the P-P Model
DME productivity of 0.49 g/gcat/h, which is 2.45 times of 80
P-M Model
experiment result from slurry reactor. In a fixed-bed reactor, 70
the corresponding levels are 10.7% and 91.9% (Lu et al., 60
XCO(%)

2002). Obviously, the fluidized-bed reactor demonstrates a 50

considerable DME productivity improvement over both the
fixed bed and the slurry reactor. Therefore, one can conclude
that the fluidized bed is the most promising candidate reactor
for conducting the DME synthesis from syngas.
5.2. Model comparison
Figs. 3–5 show the comparison of simulation results
from P–P and P–M model with experimental results. Un-
der different conditions, such as the variation of feed gas
composition, pressure, and temperature, P–M model re-
sults can be in better accordance with experimental results.
Moreover, from these figures, it can also be seen that at low
feed gas conversion, both models can simulate practical re-
actor very well, but at higher conversion, the difference of
simulation results adopting P–P or P–M model becomes re-
markable, because at low conversion, more feed gas passes
through the reactor in bubble phase, and the effect of feed
gas in dense phase is not significant, but at higher con-
version, the function of feed gas in dense phase becomes
important, thus different assumption of gas flow type in
dense phase will result in different simulation results.
40
30
20
10
0
250 260 270
T(oC)
Fig. 5. Effect of temperature on simulation and experiment results:
H2 /CO = 1, P = 3 MPa, SV = 3000 ml/gcat/h.
5.3. Effect of feed composition (H2 /CO)
Based on P–M model, Fig. 6 shows the effect of feed
composition (H2 /CO) on the reactor performance, which
demonstrates that the optimum H2 /CO ratio is about 1.4, in
accordance with the simulation results of Peng et al. (1999)
who attributes it to a trade-off between the optimum syngas
composition for methanol synthesis and that for the synergy
(i.e., methanol dehydration). Methanol synthesis is favored
by a H2 -rich environment with the maximum rate at H2 : CO
of 2:1. The dehydration reaction, on the other hand, is fastest
5462 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464

100 0.6 100 0.6

90 90
0.5 0.5
80 80
70 70

PDME(g/gcat/h)
0.4

PDME(g/gcat/h)
0.4
60 60

%
50 0.3
%

50 0.3
40 40
0.2 XCO 0.2
30 30
SDME
20 XCO 20 XCO (Equil)
0.1 0.1
SDME 10 PDME
10
PDME 0 0.0
0 0.0 270
250 260 280 290 300
0.5 1.0 1.5 2.0 2.5
H2/CO T(oC)

Fig. 8. Effect of temperature on reactor performance

Fig. 6. Effect of H2 /CO in feed gas on reaction results:
H2 /CO = 1, SV = 3000 ml/gcat/h, P = 3 MPa.
SV = 3000 ml/gcat/h, P = 3 MPa, T = 260 ◦ C.
synthesis especially and the whole reaction as well. In addi-
tion, because methanol dehydration reaction approaches to
100 0.6 equilibrium catalyzed by HZSM-5 catalyst, DME selectivity
90 keeps a high level with the increase in pressure.
0.5
80
70 5.5. Effect of reaction temperature (T)
0.4
PDME(g/gcat/h)

60
The effect of temperature is shown in Fig. 8, which re-
50 0.3
%

veals that with the increase of temperature, there exists an

40 optimum temperature for CO conversion and DME produc-
0.2
30
XCO tivity between 280 and 290 ◦ C. The existence of optimum
20 SDME 0.1 is partly due to the declining equilibrium value of CO con-
10 PDME version with temperature increasing, and more due to the
0 0.0 synergy of the different methanol synthesis and methanol
1 2 3 4 5 dehydration catalyst component with different active tem-
P(MPa) perature region. But it should be noted that the catalyst has
to be exposed to lower temperatures, less than 270 ◦ C, to
Fig. 7. Effect of pressure on reaction results: avoid excessive deactivation.
SV = 3000 ml/gcat/h, H2 /CO = 1, T = 260 ◦ C.
Moreover, DME selectivity increases a little, because
higher temperature is more favorable for the activity of
methanol dehydration catalyst rather than methanol synthe-
in a CO-rich environment, because of the low water level. sis catalyst.
The net effect of this trade-off is the shift of the optimal
H2 : CO ratio from 2:1 for syngas-to-methanol to between
5.6. Effect of space velocity (SV)
2:1 and 1:1 for syngas-to-DME.
The synergy shows that, with the increase of H2 /CO ratio,
Fig. 9 shows that, with the increase of space velocity, CO
methanol synthesis reaction is accelerated, which leads to
conversion keeps decreasing, and DME productivity remains
higher CO conversion; however, the increase of H2 /CO ratio
increasing. In addition, DME selectivity slightly decreases,
suppresses water gas shift reaction which produces H2 and
because higher space velocity means shorter residence time
consumes H2 O. Because H2 O is the product of methanol
of reactants in contact with the catalysts, and short residence
synthesis and dehydration reaction, the increase of H2 /CO
time is unfavorable for DME selectivity because DME is
ratio results in the accumulation of H2 O and decreases DME
the final product of the consecutive reactions of methanol
selectivity finally.
synthesis and methanol dehydration.

5.4. Effect of reactor pressure (P)

6. Conclusions
As is shown in Fig. 7, increasing the pressure results in an
increase in CO conversion and DME productivity, because The preliminary experimental results in this work have
the increase of pressure accelerates the reaction of methanol shown that fluidized bed technology is more efficient for
 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464 5463

100 0.8 (Hbd )b interphase heat-transfer coefficient between

90 bubble and dense phase based on bubble vol-
ume, J/m3 s K
80
0.6 (Kbd )ib overall mass-transfer coefficient (bubble
70
phase–dense phase) based on bubble volume,

PDME(g/gcat/h)
60 s−1
0.4 N
%

50 gas flow rate, mol/s

40 P reactor pressure, bar
30 PDME DME productivity, g/g/h
XCO 0.2
20 SDME Q gas volumetric flow, m3 /s
10 PDME r reaction rate, mol/gcat/s
0 0.0 SDME DME selectivity in organic products, dimen-
3000 4000 5000 6000 7000 8000 9000 sionless
Space velocity (ml/gcat/h) SV space velocity, ml/g/h
T reaction temperature, ◦ C
Fig. 9. Effect of space velocity on reactor performance
u gas velocity, m/s
H2 /CO = 1, P = 3 MPa, T = 260 ◦ C.
u0 superficial gas velocity, m/s
x mole fraction, dimensionless
XCO CO conversion, dimensionless
DME synthesis than slurry reactor and fixed-bed technology. z distance along bed height, m
When H2 /CO=1.0, the CO conversion and DME selectivity
H heat of reaction, J/g mol
are 48.5% and 97% in a fluidized-bed reactor, compared to
the values of 17% and 70% in a slurry reactor under the Greek letters
same conditions, and those of 10.7% and 91.9% in a fixed-
bed reactor under its normal conditions. ij stoichiometric coefficient of component i in
A new mechanism and kinetics model for DME synthesis reaction j , dimensionless
are established and have been applied for the simulation  equilibrium degree, dimensionless
of fluidized-bed reactor. Two two-phase models are used
bubble-phase volume as a fraction of total
to simulate DME synthesis in the lab fluidized-bed reactor bed volume, dimensionless
with the bubble phase assumed to be in plug flow, and the  dense-phase voidage, dimensionless
dense phase in plug flow (P–P model) and in fully back-  density, kg/m3
mixed flow (P–M model). Comparison between calculated  viscosity,Pa*s
and experimental results shows P–M is more valid than P–P
model. Subscripts
Then, based on P–M model, the influences of different
factors, such as pressure, temperature, H2 /CO ratio in feed b bubble phase
gas and space velocity are simulated and analyzed. The re- d dense phase
sults include that the optimum H2 /CO ratio in feed gas is f gas flow
about 1.4, and enhancement of pressure and space velocity mf minimum fluidization
improve DME productivity remarkably. There exists an op- p catalyst particle
timum temperature value between 280 and 290 ◦ C, but high
temperature may lead to excessive deactivation of the cata-
lysts. References

Brown, D.M., Bhatt, B.L., Hsiung, T.H., 1991. Novel technology for the
synthesis of dimethyl ether from syngas. Catalysis Today 8, 279–304.
Notation Bussche, K.M.V., Froment, G.F., 1996. A Steady-state kinetic model for
methanol synthesis and the water gas shift reaction on a commercial
Cu/ZnO/Al2 O3 catalyst. Journal of Catalysis 161, 1–10.
A cross-sectional area of bed, m2 Du, M.X., Li, Y.W., Hu, H.M., et al., 1993. Study on the process and
d diameter, m kinetics of synthesis of methanol and dimethyl ether from CO + H2 :
dt reactor diameter, m Part II. Kinetic model. Coal Conversion 16 (4), 68–75 (in Chinese).
Dim diffusivity of component i in gas mixture, Fernandes, F.A.N., Lona, L.M.F., 2001. Fluidized-bed reactor modeling
for polyethylene production. Journal of Applied Polymer Science 81,
m2 /s
321–332.
Dij diffusivity of component i in component Guo, J.W., Niu, Y.Q., Zhang, B.J., 2000. Macrokinetics study on DME
j, m2 /s synthesis from syngas in slurry reactor. Natural Gas Chemical Industry
H reactor height, m 25(4–7) (in Chinese).
5464 W.-Z. Lu et al. / Chemical Engineering Science 59 (2004) 5455 – 5464
Herman, R.G., Klier, K.J., 1979. Catalytic synthesis of methanol from
carbon monoxide/hydrogen. Journal of Catalysis 56 (3), 407–429.
Kunii, D., Levenspiel, O., 1969. Fluidization Engineering, first ed. Wiley,
New York.
Kunii, D., Levenspiel, O., 1991. Fluidization Engineering, second ed.
Butterworth, Boston.
Li, X., 2004. Study on the catalysis and kinetics for direct synthesis of
dimethyl ether from syngas. Master Dissertation of ECUST, vol 31–32
(in Chinese).
Lu, W.Z., Teng, L.H., Xiao, W.D., 2002. Simulation analysis of fixed-bed
reactor for dimethyl ether synthesis. Natural Gas Chemical Industry
27 (4), 53–61 (in Chinese).
Lu, W.Z., Teng, L.H., Xiao, W.D., 2003. Theoretical analysis of fluidized-
bed reactor for dimethyl ether synthesis from syngas. International
Journal of Chemical Reactor Engineering 1, S2.
Nakatsuji, H., Hu, Z.M., 2000. Mechanism of methanol synthesis on
Cu(100) and Zn/Cu(100) surfaces: comparative dipped adcluster model
study. International Journal of Quantum Chemistry 77 (1), 341–349.
Neophytides, S.G., Marchi, A.J., Froment, G.F., 1992. Methanol synthesis
by means of diffuse reflectance infrared Fourier transform and
temperature-programmed reaction spectroscopy. Applied Catalysis A
86 (1), 45–64.
Ng, K.L., Chadwick, D., Toseland, B.A., 1999. Kinetics and modelling
of dimethyl ether synthesis from synthesis Gas. Chemical Engineering
Science 54, 3587–3592.
Peng, X.D., Toseland, B.A., Tijm, P.J.A., 1999. Kinetic understanding
of the chemical synergy under LPDMETM conditions-once-through
applications. Chemical Engineering Science 54, 2787–2792.
Sun, Q., Liu, C.W., Pan, W., Zhu, Q.M., Deng, J.F., 1998. In situ IR
studies on the mechanism of methanol synthesis over an ultrafine
Cu/ZnO/Al2 O3 catalyst. Applied Catalysis A 171 (2), 301–308.
Wagialla, K.M., Elnashaie, S.S.E.H., 1991. Fluidized-bed reactor
for methanol synthesis: a theoretical investigation. Industrial &
Engineering Chemistry Research 30, 2298–2308.
Wang, Z.L., Wang, J.F., Diao, J., Jin, Y., 2001. The synergy effect
of process coupling for dimethyl ether synthesis in slurry reactors.
Chemical Engineering & Technologies 24 (5), 507–511.
Werther, J., 1980. Mathematical modeling of fluidized bed reactors.
International Chemical Engineering 20, 4.
Xiao, W.D., Lu, W.Z., 2002. A novel technology of DME synthesis from
syngas. CN1332141.
Zhang, H.T., Cao, F.H., Liu, D.H., Fang, D.Y., 2001. Thermodynamic
analysis for synthesis of dimethyl ether and methanol from synthesis
gas. Journal of ECUST 27 (2), 198–201 (in Chinese).