EQUILIBRIUM CALCULATIONS FOR DIRECT SYNTHESIS OF

DIMETHYL ETHER FROM SYNGAS

G. R. Moradi,1 * J. Ahmadpour,2 F. Yaripour3 and J. Wang4
1. Catalyst Research Center, Faculty of Engineering, Department of Chemical Engineering, Razi University, Kermanshah, Iran
2. Chemical Engineering Department, Babol University of Technology, P.O. Box 484, Babol, Iran
3. Catalysis Research Group, Arak Center of Petrochemical Research & Technology Co., National Petrochemical Company
(NPC), P.O. Box 1493, Arak, Iran
4. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering,
Tsinghua University, Beijing 100084, China

Thermodynamic analysis of single-step synthesis of dimethyl ether (DME) from syngas over a bi-functional catalyst (BFC) in a slurry bed reactor
has been investigated as a function of temperature (200240 C), pressure (2050 bar), and composition feed ratio (H2 /CO: 12). The BFC
was prepared by physical mixing of CuO/ZnO/Al2 O3 as a methanol synthesis catalyst and H-ZSM-5 as a methanol dehydration catalyst. The
three reactions including methanol synthesis from CO and H2 , methanol dehydration to DME and watergas shift reaction were chosen as the
independent reactions. The equilibrium thermodynamic analysis includes a theoretical model predicting the behaviour and a comparison to
experimental results. Theoretical model calculations of thermodynamic equilibrium constants of the reactions and equilibrium composition of all
components at different reaction temperature, pressure, and H2 /CO ratio in feed are in good accordance with experimental values.

Lanalyse thermodynamique de la synth`ese en une e tape du methoxymethane du gaz de synth`ese sur un catalyseur bifonctionnel dans un reacteur
a` lit bouillonnant a e te e tudiee comme une fonction de temperature (200 a` 240 C), de pression (20 a` 50 bars) et de rapport dalimentation
compositionnel (H2/CO: 12). Le catalyseur bifonctionnel e tait prepare par un melange physique de CuO/ZnO/Al2O3 comme un catalyseur de
synth`ese de methanol et de H-ZSM-5 comme un catalyseur de deshydratation du methanol. Les trois reactions, soit la synth`ese du methanol du
CO et du H2, la deshydratation du methanol en methoxymethane et la conversion catalytique, ont e te choisies comme reactions independantes.
Lanalyse thermodynamique de lequilibre comprend un mod`ele theorique qui predit le comportement et une comparaison par rapport aux resultats
experimentaux. Les calculs du mod`ele theorique des constantes de lequilibre thermodynamique des reactions et la composition dequilibre de
tous les composants a` differentes temperatures de reaction, differentes pressions et un different rapport H2/CO dans lalimentation cadrent bien
avec les valeurs experimentales.

Keywords: dimethyl ether, syngas, slurry reactor, thermodynamic modelling

INTRODUCTION tions in the STD process can be shown as follows (Wang et al.,
2006):

D
imethyl ether (DME) is not only an important chemi-
cal material, but also a potential clean fuel substitute for
LPG and diesel fuel. DME also can be used as an excel-
lent propellant and refrigerant. It is an important feedstock for
Additional Supporting Information may be found in the online version of
the preparation of light alkenes too (Ng et al., 1999; Nie et al., this article.
2005). At present, DME is commercially prepared by dehydra- Author to whom correspondence may be addressed.
tion of methanol using acidic porous catalysts such as zeolites, E-mail address: gmoradi@razi.ac.ir
silicaalumina, alumina, etc. Recently, an original technique Can. J. Chem. Eng. 89:108115, 2011
named synthesis gas to DME (STD) process was developed for 2010 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20373
the direct synthesis of DME from synthesis gas in a single reactor Published online 9 November 2010 in Wiley Online Library
on bi-functional catalysts (BFC, Xia et al., 2004). The main reac- (wileyonlinelibrary.com).

| 108 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, FEBRUARY 2011 |
 Methanol synthesis (CO hydrogenation) milled and sieved to sizes less than 90 m, and well mixed at
mass ratio 3:1. Then the mixture was molded under pressure
CO + 2H2 CH3 OH 90.4kJ/mol (1) into tablets, which were then crushed and sieved to 90120 mesh
size particles in order to avoid pore diffusional limitations. The
Methanol dehydration description in detail about characterization test of catalyst such
as TPR, XRD, XRF, and BET could be found elsewhere (Moradi et
CH3 OH CH3 OCH3 + H2 O 23.0kJ/mol (2) al., 2007, 2008a,b,c,d,e).

Watergas shift
Experimental Set-Up and Catalytic Tests
CO + H2 O CO2 + H2 41.0kJ/mol (3) A schematic view of the lab scale setup is shown in elsewhere
(Moradi et al., 2007, 2008a,b,c,d,e). In brief, the STD reaction
Methanol synthesis (CO2 hydrogenation) thermodynamic study was carried out in a 1L mechanically
agitated slurry reactor, equipped with four bladed impeller
CO2 + 3H2 CH3 OH + H2 O 49.4kJ/mol (4) and withstanding temperatures up to 300 C and pressures of
100 bar, in which the 10.5 g catalyst was suspended in 350 g
Overall reaction liquid parafn (treated to remove any trace poisons before
use) with boiling point of higher than 305 C. Before each test,
3CO + 3H2 CH3 OCH3 + CO2 258.312kJ/mol (5) the catalyst had been reduced and active ex situ with pure
hydrogen at the normal pressure according the following heating
The number of independent reactions in the DME synthesis program: heated from room temperature to 250 C with heating
process is 3. Reaction No. 4 (CO2 hydrogenation) can be easily rate 1 C/min and was kept for 6 h at this temperature. Then
obtained by summation of reactions 1 and 3 and cannot be con- the catalysts were cooled to room temperature at the presence
sidered as an independent reaction. When these reactions take of hydrogen ow. After this pretreatment, the feed (H2 :CO:N2 )
place within one reactor using BFC, the equilibrium conversion was introduced into the slurry reactor. A small portion of the
of syngas improves signicantly due to the synergic effect between reactor efuent was sent to gas chromatograph (GC) for on line
reactions (Li et al., 1996). analysis. Varian CP-3800 GC equipped with two packed columns:
There are some theoretical articles reporting the thermody- HaySep Q (80100 mesh, 2 m 1/8 2.0 mm, SS), Chrompach
namic behaviour of DME synthesis either from CO hydrogenation Molecular Sieve 13 (80100 mesh, 2 m 1/8 2.0 mm,
(Grzesik and Skrzypek, 1999; Zhang et al., 2001; Jia et al., 2006; SS) for separating CO2 , H2 , N2 , CO, and MeOH, DME,
Wang et al., 2006b), or CO2 hydrogenation (Kulawska et al., 2000; CH4 , respectively, and detecting by a thermal conductivity
Meshcheryakov, 2000; Shen et al., 2000) or two processes simul- detector.
taneously (Grzesik et al., 2000; Jia et al., 2006) but in a few papers
theoretical results have been compared with the experimental data Experimental Conditions
(Wang et al., 2004). However, there is not a comprehensive ther-
In order to close to equilibrium conditions, the inuence of space
modynamic analysis on this process. A thermodynamic modelling
velocity in three H2 /CO ratios on CO conversion at 513 K and
is essential for prediction the equilibrium behaviour of the pro-
35 bar, has been studied by decreasing space velocity from 1500
cess with variation of operating conditions as the upper limit of
the possible progression of the reaction.
In this work, a thermodynamic equilibrium model which can
predict thermodynamic behaviour in the direct synthesis of DME
over a BFC (CuO-ZnO-Al2 O3 /H-ZSM-5) in the slurry phase reactor
was developed which can provide reliable basic data for sim-
ulations and engineering applications. Moreover, the effects of
reaction temperature, pressure, mole ratio of H2 /CO in the reac-
tant mixture have been investigated. This study carried out in
the slurry reactor. So, more reliable thermodynamic data can be
obtained because of good temperature control that enables exper-
iments at near isothermal conditions regardless of reaction heats
and rates. Small catalyst particles can be used to eliminate intra-
particle mass transfer effects. Slurry stirred tank reactors have
come to common use for methanol and DME synthesis studies
(Peng et al., 1999).

EXPERIMENTAL
Catalyst
Bi-functional catalyst was prepared by admixing of the two
catalysts, commercial methanol synthesis catalyst (manufac-
tured by KMT: Ul. Vilesova, 1 Lugansk region, Severodonetsk,
93400 Ukrain) and methanol dehydration catalyst (supplied by

Sud-Chemie:
Sud-Chemie AG Lenbachplatz 6 80333 Munich, Ger- Figure 1. CO conversion as a function of space velocity and feed gas
many), namely H-ZSM-5. Two commercial catalysts were nely H2 /CO ratio, P = 3.5 MPa, T = 240 C.

| VOLUME 89, FEBRUARY 2011 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 109 |
to 300 mL/(g-cat/h), in the slurry bed reactor (Moradi et al., Fin yCO,in Fout yCO,out
XCO = (6)
2008c). The results are shown in Figure 1. In each of the three Fin yCO,in
feeds composition, CO conversion increases with decreasing space
velocity until reaches to its maximum value at about 500 mL/(g- Fin yH2 ,in Fout yH2 ,out
X H2 = (7)
cat/h) and no longer increases with decreasing space velocity, Fin yH2 ,in
indicating that there is no driving force for more progress of the
reactions. Its mean that at the space velocity less than 500 mL/(g- 2Fout yDME,out
YDME = (8)
cat/h), the exit gas mixture has been reached to thermodynamic Fin yCO,in
equilibrium. This observation provides the basis for choosing the
operational conditions for measuring thermodynamic equilibrium 2Fout yDME,out
SDME = (9)
data. The kinetics of DME synthesis could be studied at a space Fin yCO,in Fout yCO,out
velocity [1100 mL/(g-cat/h)] which is sufciently far from equi-
librium conditions, since the data are sensitive to the reaction Fout yCO2 ,out
SCO2 = (10)
kinetics of DME synthesis, and close enough that synergy in DME Fin yCO,in Fout yCO,out
synthesis is signicant. The experiments were always carried out
under steady-state condition. This state was achieved within 20 h THEORETICAL ANALYSIS
from start up. Mass and heat transfer limitations were negligi-
ble during the chosen experimental conditions. At a 3 (wt%) Calculation of Chemical Equilibrium Constants
slurry (corresponding to 10.5 g of catalyst per 350 g of solvent) At the constant pressure, the equilibrium constants of reactions
in a mechanically agitated slurry reactor, the gasliquid mass (13) are only a function of temperature. The temperature depen-
transfer does not limit the overall rate. Also, in preliminary exper- dence of the thermodynamic equilibrium constant is given by
iment it was checked for the external mass transfer limitation: Vant Hoffs equation (Zhang et al., 2001; Wang et al., 2006b):
above 1500 rpm of impeller speed, no mass transfer resistances
were found. To assure that gasliquid mass transfer limitations dLn Kf HR0
were absent, the experimental was carried out at 1600 rpm. In = (11)
dT RT 2
the LPDME process, the real driving force for reactants should be
the reactant concentration in liquid. But because of the absence of By integration of Vant Hoffs equation, we have:
both the internal and external mass transfer resistances as the con-
 T
trol step, it may be assumed that the species concentrations at the HR0
surface were assumed to be the same as those in the bulk liquid LnKf LnKf,298.15K = dT (12)
298.15K RT 2
phase and the gas phase and the liquid phase to be in thermody-
namic equilibrium (Graaf et al., 1988; Setinc and Levec, 1999). In which, Kf,298.15K is equilibrium constant under the ideal gas
So, no deference would be found whether the model equations state and can be calculated as follows:
are expressed in terms of liquid concentration or partial pressure.
0
Then it would be logical to base the thermodynamic calculations Gf,298.15K
LnKf,298.15K = (13)
on the gas phase. Besides conversion, effects of space velocity 298.15R
on the other LPDME process responses such as yield and selec-
0
tivity of DME, investigated in our pervious study, indicate that where Gf,298.15K is the standard free energy of formation.
near the equilibrium condition, the increase of these responses The standard heat of reaction HR0 is a function of temperature.
with decreasing space velocity slows down due to the equilibrium The effect of temperature on HR0 is given by:
state (Moradi et al., 2008c). Furthermore, according to the results
  
of our previous works (Moradi et al., 2008a,d), our BFC has a very T 
good stability in our experimental condition. The outstanding cat- HR0 = 0
HR,298.15 + 0
i CP,i dT (14)
298.15 i
alytic performance is owing to high activity of metallic function
(CuO-ZnO-Al2 O3 ) and suitable acidity of acidic partner (H-ZSM-5 0
In which HR,298K is the standard reaction heat at 298.15 K, and
zeolite) which creates a strong chemical synergy effect for reaction 0
CP,i is the constant pressure heat capacity of species i in its stan-
system by a useful interaction between the two of these functions.
dard state. The ideal-gas isobaric heat capacity could be obtained
Furthermore, the moderate acid strength of dehydration compo-
from the following correlation:
nent (H-ZSM-5) is a key factor that minimises side reactions of
transformation of MeOH and DME into hydrocarbons which even- 0
CP,i = A + BT + CT 2 + DT 3 (J/mol/K) (15)
tually deposit on catalyst as coke and deactivate it. Consequently,
the performance of this catalyst makes it suitable for industrial
The values of the related coefcients could be obtained from
use in the synthesis of DME from syngas. In order to generate
Reids thermodynamic data (Reid et al., 1987). When the val-
data for validation of thermodynamic modelling, a broad range of
ues given in Table 1 for the standard properties of formation at
experimental conditions have been performed under the follow-
298.15 K, and the coefcients A, B, C, and D of Equation (15),
ing thermodynamic reaction conditions: 200240 C, 2050 bar,
are used, the following expression for Kf,j is obtained (Reid et al.,
H2 /CO molar ratio from 1:1 to 2:1 and space velocity of 500 mL/(g-
1987):
cat/h). The space velocity was sufciently low such that there
was no measurable increase in conversion with decreased space Bj
velocity. For each experiment, the carbon balance over the reactor LnKf,j = Aj + + Cj LnT + Dj T + Ej T 2 + Fj T 3 (16)
T
was calculated. The average absolute deviation was less than 3%.
The conversion of CO and H2 , DME selectivity and yield and CO2 A calculation program has been developed for determining the
selectivity are dened as follows: values of Aj Fj , coefcients of the equilibrium constants for each

| 110 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, FEBRUARY 2011 |
 Table 1. Pure component gas phase standard properties of formation (kJ/mol) at 298.15 K and coefcients of the heat capacity correlation, for the
calculation of K by Equation (15)

Component Hf,298.15
0
(kJ/mol) Gf,298.15
0
(kJ/mol) CP,i
0
= A + BT + CT 2 + DT 3 (J/mol/K)

H2 0 0 27.1 9.27 103 1.38 105 7.65 109

CO 111 137 30.9 1.29 102 2.79 105 1.27 108
CO2 394 395 19.8 7.34 102 5.60 105 1.72 108
CH3 OCH3 184 113 17 1.79 101 5.23 105 1.92 109
CH3 OH 201 163 21.2 7.09 102 2.59 105 2.85 108
H2 O 242 229 32.2 1.92 103 1.06 105 3.60 109

Table 2. Coefcients of Equation (16) for the calculation of equilibrium constants of the three reactions that comprise the original set of linearly
independent reactions (given in Introduction Section)

Reaction Aj Bj Cj Dj Ej Fj

(1) 22.67 8.984 103 7.964 3.92 103 5.127 107 3.114 1010
(2) 9.37 3.196 103 0.835 2.349 103 1.873 106 5.161 1010
(3) 5.074 4.771 103 1.944 5.628 103 2.169 106 4.118 1010

reaction as shown in Table 2. The values of the equilibrium (ya a )(yc c ) (yf f )(yb b )Kf,3 = 0 (23)
constants for each reaction at certain temperature with new ther-
modynamic equilibrium model are consistent with those recorded In which the components in the reacting system are identied
by formers studies (Wang et al., 2004) especially with Aguayo et by the following subscripts: H2 (a), CO (b), CO2 (c), CH3 OCH3
al. (2007). (d), CH3 OH (e), and H2 O (f). The fugacities of the components
must also be known in order to calculate the equilibrium compo-
Calculation of the Fugacity Coefcients sition. The fugacity of each component was calculated by SHBWR
The chemical equilibrium constant Kf,j for reaction j of a multiple- and SRK equations of state. Calculation showed that the differ-
reaction system is given by the expression: ence between the reaction fugacity and the corresponding partial
pressure of each component was very small under the reaction
  j 
C
conditions of interest (Moradi et al., 2008b). So, the six par-
P
Kf,j = (yi i )i,j (17) tial fugacity coefcients those are required in Equations (2123)
P0
i=1 could be obtained by application of the SRK equation of state that
is commonly used for calculating of the fugacity coefcients of
where yi is the equilibrium mole fraction, i is the fugacity coef- the component in the DME and methanol synthesis from syngas
cient of the component i, and i,j is the stoichiometric coefcients system. The SRK equation of state is as follows:
(positive for products and negative for reactants) of each of the C
species involved in the reaction j, P is the pressure of the system, RT a(T)
P0 = 1 bar is the standard pressure, and p= (24)
V b V(V + b)

 j = i,j (18)
i The fugacity coefcient can be calculated from another expres-
sion as:
The equilibrium mole fraction yi is related to the extent of reac-
tion j at equilibrium ( j ) by the expression:
   
bi A 2ai0.5 bi B
lni = (Z 1) ln(Z B) ln 1 +
r b B a0.5 b Z
Fi,0 + i,j j
yi = rj=1 (19) (25)
F0 + j=1
 i j
ai P bi P
where r is the number of linearly independent reactions, Fi,0 is A= , B= (26)
the molar ow rates of species i in the feed to the reactor, and R2 T 2 RT

C The mixture compressibility factor Z is the real root of the SRK

Fo = Fi,0 (20) cubic equation of state:
i=1

For three set of linearly independent reactions (Equations 13) Z 3 Z 2 + (A B B2 )Z AB = 0 (27)

in the gas phase direct synthesis of DME from syngas, Equation
(17) leads to the following set of equations:
The parameters in this equation were evaluated using original
 2 mixing rules with interaction coefcients:
P
(ye e ) (ya a )2 (yb b ) Kf,1 = 0 (21)
P0 
n

a= yi yj aij aij = (ai aj )0.5 (1 kij ), b = yi bi (28)
(yd d )(yf f ) (ye e )2 Kf,2 = 0 (22) j=1 i

| VOLUME 89, FEBRUARY 2011 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 111 |
 Some binary interaction parameters were reported for CO, H2 ,
CH3 OH, and H2 O in heavy parafns (Graaf et al., 1992). But, by
using fugacity of each component instead of its corresponding
concentration in the liquid phase, due to thermodynamic equilib-
rium between liquid and gas phase, it is not necessary to use these
parameters. Beside, due to a lack of experimental data in the gas
phase, all kij are taken to 0 as indicated by Jia et al. (2006); and
Wang et al. (2004).
For a given value of reaction temperature T, the equilibrium
constants Kf,j of the three reactions are xed by Equation (16). If
the reaction pressure P is also xed, then Equations (2123) yield
a set of three nonlinear algebraic equations that can be solved
for the three extents of reaction at equilibrium ( j ) by using of
the NewtonRaphson method with initial guesses of unit for all
fugacity coefcients. A calculation program has been developed
to determine extend of reaction and the composition of the system
in the equilibrium.

RESULT AND DISCUSSION
Validation of the Model
Systematic calculations have been performed based on the previ-
ously mentioned methods. The results have been compared with
experimental data. So, the thermodynamic equilibrium model
using Reids thermodynamic data for calculating the equilib-
rium constants and correcting for non-ideal gas behaviour using
the SRK equation show a good agreement with the experimen-
tally obtained data. The performance of this model has been
shown in Figures 24. Therefore, this model could be chosen
for using in the thermodynamic calculations of DME synthe-
sis from syngas in slurry reactor. It must be emphasised that
these results are valid at the experimental ranges of the opera-
tional conditions. The effects of reaction temperature, pressure,
and H2 /CO mole ratio on the equilibrium state have been inves-
tigated by using this thermodynamic model in the following
sections:
Figure 3. Comparison of calculated and experimental values versus
pressure, H2 /CO = 2, T = 240 C, SV = 500 mL/(g-cat/h), () XCO , ()
YDME ; Symbols: experimental, Lines: calculated.
Effect of Temperature
Figure 5 shows the inuence of temperature on reaction equi-
librium for a pressure of 50 bar and molar ratio of H2 /CO = 2.
With increasing the reaction temperature, CO conversion, DME
yield and DME selectivity decreased, which is in accordance with
the exothermic feature of methanol synthesis and dehydration
reactions.
Effect of Pressure
Figure 6 shows the inuence of pressure on the conversion of
CO, yield of DME, and selectivity of DME and CO2 in the equi-
librium state. As is observed, when pressure is increased in
the range from 20 to 50 bar, the conversion of CO and yield of

Figure 2. Comparison of calculated and experimental values versus Figure 4. Comparison of calculated and experimental values versus
temperature, H2 /CO = 2, P = 50 bar, SV = 500 mL/(g-cat/h), () XCO , () H2 /CO, T = 240 C, P = 50 bar, SV = 500 mL/(g-cat/h), () XCO , () YDME ;
YDME ; Symbols: experimental, Lines: calculated. Symbols: experimental, Lines: calculated.

| 112 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, FEBRUARY 2011 |
Figure 5. Effect of temperature on equilibrium, H2 /CO = 2, P = 50 bar,
SV = 500 mL/(g-cat/h).
DME increases. Since the formation of methanol (reaction 1) is
a molecular-decreasing reaction and both methanol dehydration
and watergas shift reactions do not lead to change of mole num-
ber, high pressure favours methanol synthesis and gives high
methanol yield that in turn DME, but does not have much effect on
methanol dehydration. So, the increase of reaction pressure accel-
erates the reaction of methanol synthesis specially and the whole
reaction as well, that cause strong synergy between methanol syn-
thesis and dehydration reactions. It should be mentioned, synergy
in total methanol production is obtained by effective removal of
the products from the methanol synthesis reaction, that is, by
depressing the reverse reaction (Ng et al., 1999; Lu et al., 2004;
et al., 2005a; Wang et al., 2006b; Moradi et al., 2007).
Erena
Meanwhile, with the same reason, as pressure is increased, CO2
selectivity decreases and that of DME selectivity increases.
Figure 6. Effect of pressure on equilibrium, H2 /CO = 2, T = 240 C,
SV = 500 mL/(g-cat/h).
| VOLUME 89, FEBRUARY 2011 | |
Figure 7. Effect of H2 /CO on equilibrium, T = 240 C, P = 50 bar,
SV = 500 mL/(g-cat/h).
Effect of H2 /CO Feed Ratio
Effect of the feed composition (H2 /CO ratio) on the reaction equi-
librium has been investigated. With the increase of H2 /CO ratio,
CO conversion, DME yield and selectivity increase, but the H2
conversion and CO2 selectivity decrease at the same time. The
calculated results are shown in Figure 7. An increase in the pro-
portion of H2 in the reactant mixture favours CO conversion,
which is the opposite of the case for the watergas shift reaction.
The reaction order for the methanol synthesis reaction is 2, whilst
for watergas shift the reaction order is 1 (Wang et al., 2004).
Thus, with the increases of H2 /CO ratio, methanol synthesis reac-
tion is accelerated, which lead to higher CO conversion; because
of methanol synthesis, is favoured by H2 rich environment with
the maximum rate at H2 /CO feed ratio of 2:1 (Lu et al., 2004).
Meanwhile, the STD process, CO2 is the main byproduct witch is
generated by watergas shift reaction. A possibility for suppress-
ing the excess formation of CO2 is to increase the H2 /CO ratio of
the reactant syngas (Soans and Scurrell, 1991). So, by operating
at high H2 /CO ratio CO2 selectivity can be substantially decreased
with a simultaneous improvement in the DME yield and selectiv-
ity. On the other hand, H2 Conversion decreases with increasing
of H2 /CO feed ratio, namely lower concentration of H2 in the feed
lead to highest value of H2 conversion, since in this condition
H2 is the limiting reactant and watergas shift reaction is not very
important reaction, then most of H2 convert to methanol, but with
increasing of H2 content in the feed both limiting reactant shift to
CO and watergas shift reaction inhabit for more H2 conversion,
then conversion of H2 decrease with increasing of H2 /CO ratio
(Erena et al., 2005b).
CONCLUSION
In this study, a thermodynamic equilibrium model using Reids
thermodynamic data for calculating the equilibrium constants
(assuming ideal gas behaviour) and correcting for non-ideal gas
behaviour using the SRK equation was found to agree well with
experimental results over a wide range of experimental condi-
tions. The equilibrium constants for three independent reactions
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 113 |
involved in direct DME synthesis from syngas have been deter- ACKNOWLEDGEMENTS
mined in temperature range between 200 and 240 C. These
The authors acknowledge the nancial support of this work by
temperature dependence relationships for equilibrium constants
research and technology affairs of National Iranian Petrochemical
will be found useful in kinetic modelling and reactor and plant
Sunggyu Lee,
Company. We are especially grateful to Javier Erena,
design of STD process. Moreover, the effects of reaction tempera-
and Yizhuo Han for fruitful suggestions, discussions, and critical
ture, pressure, and H2 /CO ratio were investigated with thorough
remarks.
understanding of this thermodynamic model. Based on the results,
the following conclusions were drawn:

1. In direct DME synthesis, the effect of reaction synergy

is prominent and a higher conversion of CO and DME REFERENCES
yield without limiting the thermodynamic equation can be D. Mier, J. M. Arandes, M. Olazar and J.
Aguayo, A. T., J. Erena,
obtained. Bilbao, Kinetic Modeling of Dimethyl Ether Synthesis in a
2. With increasing the reaction temperature, CO conversion, Single Step on a CuO-ZnO-Al2 O3 /-Al2 O3 Catalyst, Ind. Eng.
DME yield, and DME selectivity decreased, which is in accor- Chem. Res. 46, 55225530 (2007).
dance with the exothermic feature of methanol synthesis and J., R. Garona, J. M. Arandes, A. T. Aguayo and J. Bilbao,
Erena,
dehydration reactions. Effect of Operating Conditions on the Synthesis of Dimethyl
3. When reaction pressure increases, CO conversion, DME yield, Ether over a CuO-ZnO-Al2 O3 /NaHZSM-5 Bifunctional
and DME selectivity increase. Catalyst, Catal. Today 107108, 467473 (2005a).
4. With the increase of H2 /CO ratio, CO conversion, DME yield Erena, J., R. Garona, J. M. Anderas, A. T. Aguayo and J. Bilbao,
and selectivity increase, but the H2 conversion and CO2 selec- Direct Synthesis of Dimethyl Ether From (H2 + CO) and
tivity decrease at the same time. (H2 + CO2 ) Feeds. Effect of Feed Composition, Int. J. Chem.
Reactor Eng. 3, Article A44 (2005b).
NOTATION Graaf, G. H., E. J. Stamhuis and A. A. C. M. Beenackers,
Kinetics of the Three Phase Methanol Synthesis, Chem.
a parameter in SRK equation
Eng. Sci. 43(8): 21612168 (1988).
ai,j parameter in SRK equation
Graaf, G. H., K. L. Smit, E. J. Stamhuia and A. A. C. H.
A dened constant by the corresponding equation
Beenackers, Gas-liquid solubilities of the methanol synthesie
b parameter in SRK equation
compansnte in various solvents, J. Chem. Eng. nata, 37,
B dened constant by the corresponding equation
146158 (1992).
Ai,j coefcient in heat capacity formulae
Grzesik, M. and J. Skrzypek, Chemical Equilibria in Direct
C Number of species in the reacting mixture
Synthesis of Dimethyl Ether, Stud. Surf. Sci. Catal. 122,
CP0 isobaric heat capacity (J/mol/K)
411414 (1999).
f Fugacity (bar)
Grzesik, M., A. Ptaszek and J. Skrzypek, Equilibrium
F Molar ow rate (mol/s)
0 Conversion Degree in Direct Synthesis of Dimethyl Ether
Gf,298.15K standard free energy of formation (J/mol)
From CO and H2 , Ind. Chem. Proc. 21, 725732 (2000).
HR0 standard reaction heat (J/mol)
0 Jia, G. X., Y. Tan and Y. Han, A Comparative Study on the
Hf,298.15K standard heat of formation (J/mol)
Thermodynamics of Dimethyl Ether Synthesis From CO
Kf equilibrium constant
Hydrogenation and CO2 Hydrogenation, Ind. Eng. Chem.
Kf,298.15K equilibrium constant under the ideal gas state
Res. 45, 11521159 (2006).
P pressure (bar)
Kulawska, M., J. Skrzypek and M. Grzesik, The Effect of
P0 atmospheric pressure (bar)
Process Parameters on the Equilibrium Dimethyl Ether Yield
Pc critical pressure
in Its Direct Synthesis From CO2 and H2 , Przem. Chem.
R gas constant (8.314J/mol/K)
79(7), 231233 (2000).
SDME selectivity of DME
Li, J. L., X. G. Zhang and T. Inui, Improvement in the Catalyst
SCO2 selectivity of CO2
Activity for Direct Synthesis of Dimethyl Ether From
SV space velocity (mL/(g-cat/h))
Synthesis Gas Through Enhancing the Dispersion of
T temperature (K)
CuO/ZnO/-Al2 O3 in Hybrid Catalysts, Appl. Catal. A: Gen.
Tc critical temperature
147(1), 2333 (1996).
V gas volume (m3 )
Lu, W. Z., L. H. Teng and W. D. Xiao, Simulation and
W weight of catalyst (g)
Experiment Study of Dimethyl Ether Synthesis From Syngas
XCO CO conversion
in a Fluidized-Bed Reactor, Chem. Eng. Sci. 59, 54555464
XH 2 H2 conversion
(2004).
YDME yield of DME
Meshcheryakov, V. D., Thermodynamic Equilibrium in the
y mole fraction
Synthesis of Dimethyl Ether From Synthesis Gas, Theor.
Z compressibility factor
Found. Chem. Eng. 34(1), 8589 (2000).
Moradi, G. R., R. Ghanei and F. Yaripour, Determination of the
Greek Symbols Optimum Operating Conditions for LPDME From Syngas,
Fugacity coefcient Int. J. Chem. React. Eng. 5, Article A14 (2007).
 extent of reaction Moradi, G. R., M. Nazari and F. Yaripour, Statistical Analysis of
vij stiochoimetric coefcient of component i involved the Performance of a Bi-Functional Catalyst Under Operating
in chemical reacton j Conditions of LPDME Process, Chem. Eng. J. 140, 255263
acentric factor (2008a).

| 114 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, FEBRUARY 2011 |
Moradi, G. R., J. Ahmadpour and F. Yaripour, Intrinsic Kinetics
Study of LPDME Process From Syngas Over Bi-Functional
Catalyst, Chem. Eng. J. 144, 8895 (2008b).
Moradi, G. R., J. Ahmadpour, M. Nazari and F. Yaripour, Effects
of Feed Composition and Space Velocity on Direct Synthesis
of Dimethyl Ether From Syngas, Ind. Eng. Chem. Res. 47,
76727679 (2008c).
Moradi, G. R., M. Nazari and F. Yaripour, The Interaction
Effects of Dehydration Function on Catalytic Performance and
Properties of Hybrid Catalysts Upon LPDME Process, Fuel
Process Technol. 89, 12871296 (2008d).
Moradi, G. R., J. Ahmadpour and F. Yaripour, Systematic
Investigation the Effects of Operating Conditions on LPDME
Process, Energy Fuels 22, 35873593 (2008e).
Ng, K. L., D. Chadwick and B. A. Toseland, Kinetics and
Modeling of Dimethyl Ether Synthesis From Synthesis Gas,
Chem. Eng. Sci. 54, 35873592 (1999).
Nie, Z., H. Liu, D. Liu, W. Ying and D. J. Fang, Intrinsic
Kinetics of Dimethyl Ether Synthesis From Syngas, Nat. Gas
Chem. 14, 2228 (2005).
Peng, X. D., B. A. Toseland and P. J. A. Tijm, Kinetic
Understanding of the Chemical Synergy Under LPDMETM
Conditions Once-Through Applications, Chem. Eng. Sci. 54,
27872792 (1999).
Reid, R. C., J. M. Prausnitz and B. E. Poling, The Properties of
Gases and Liquids, 4th ed., McGraw-Hill, New York (1987),
pp. 656732.
Setinc, M. and J. Levec, On the Kinetics of Liquid-Phase
Methanol Synthesis over Commercial Cu/ZnO/Al2 O3
Catalyst, Chem. Eng. Sci. 54, 35773586 (1999).
Shen, W. J., K. W. Jun, H. S. Choi and K. W. Lee,
Thermodynamic Investigation of Methanol and Dimethyl
Ether Synthesis From CO2 Hydrogenation, Korean J. Chem.
Eng. 17, 210216 (2000).
Soans, A. C. and M. S. Scurrell, Conversion of Synthesis Gas to
Dimethyl Ether Over Bifunctional Catalytic Systems, Ind.
Eng. Chem. Res. 30, 23722378 (1991).
Wang, Z., J. Wang, F. Ren, M. Han and Y. Jin, Thermodynamics
of the Single-Step Synthesis of DME From Syngas, Tsinghua
Sci. Technol. 9(2), 168176 (2004).
Wang, L., D. Fang, X. Huang, S. Zhang, Y. Qi and Z. Liu,
Inuence of Reaction Conditions on Methanol Synthesis and
WGS Reaction in the Syngas to DME Process, J. Nat. Gas
Chem. 15, 3844 (2006a).
Wang, Z., J. Diao, J. Wang and Y. Jin, Study on Synergy Effect
in Dimethyl Ether Synthesis From Syngas, Chin. J. Chem.
Eng. 9(4), 412416 (2006b).
Xia, J., D. Mao, B. Zhang, Q. Chen and Y. Tang, One Step
Synthesis of Dimethyl Ether From Syngas With Fe-Modied
Zeolite ZSM-5 as Dehydration Catalyst, Catal. Lett. 98,
235240 (2004).
Zhang, H. T., F. H. Cao, D. H. Liu and D. Y. Fang,
Thermodynamic Analysis4 for Synthesis of Dimethyl Ether
and Methanol From Synthesis Gas, J. ECUST 27(2), 198201
(2001).

Manuscript received October 16, 2009; revised manuscript

received January 15, 2010; accepted for publication January 20,
2010.

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