and

Direct
TruckKinetic
Application
Route Model
Dimethyl
of Asphalt
Ether Synthesis
Concretefrom

Direct Dimethyl Ether Synthesis from

Mixture
Synthesis
usingGas:

Synthesis Gas: Experiments and

AC Experiments
40-50 in

Kinetic Model
P. Ratamanalaya1
S. Limtrakul2
T. Vatanatham2
P. A. Ramachandran3

Abstract

Dimethyl ether is a clean alternative of exothermic reaction, there is a maximum
diesel fuel which can be produced directly
conversion at the temperature of 265 C. In
from synthesis gas. The performance of
addition, the conversion decreases with increasing
direct dimethyl ether synthesis from synthesis
space velocity due to decreasing reaction

gas using a bi-functional catalyst (CuO-ZnO-
time. The kinetic models were developed and
Al 2O 3/HZSM-5) in a fixed bed reactor was kinetic parameters were estimated from

experimentally investigated at various pressures the experimental data. Calculations of DME
(20-50 bars), temperature (245-275 C), and synthesis performance with the developed
space velocities (1,958-23,099 ml/g cat-h STD). kinetic correlations were accomplished. The
The synthesis gas conversion increases with calculated and experimental results agree well
increasing pressure and temperature. However, with the experimental data.
with thermodynamic equilibrium limitation

1
Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok, 10900, Thailand
2
National Center of Excellence for Petroleum, Petrochemical and Advanced Materials, Department of Chemical
Engineering, Faculty of Engineering, Kasetsart University, Bangkok, 10900, Thailand
3
Department of Energy, Environmental & Chemical Engineering, Washington University, St. Louis, USA

64
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 Keywords: dimethyl ether synthesis, Overall reaction:
kinetic models, fixed bed 3CO + 3H2 CH3OCH3 + CO2 (4)

Introduction Reactions in Eq. 1 and 2 are catalyzed
by a methanol synthesis catalyst such as Cu/
Dimethyl ether (DME, CH3OCH3) has Zn, Zn/A1, Zn/Cr, Cu/Zn/A1, Cu/Zn/Cr, Cu/Zn/
been known as a clean substituting fuel for Co, or Cu/Cr/Fe and Reaction in Eq. (3) is
diesel engine due to high cetane number and catalyzed by an acidic component such as -
no SOx or NOx emission after combustion [1-4]. alumina, silica-aluminas, aluminas, or zeolites
DME is a liquid under modest pressure (6.1 atm [4-8]. These three reactions form a synergic
at 25 C) [2] thus it is relatively easy to store and system yielding higher synthesis gas conversion
transport. DME can be produced from synthesis (Eq. 4) compared to the synthesis gas-to
gas (CO and H2) in a one-step process instead methanol-process (Eq. 1) [3]. Methanol created
of a two-step process. In the two-step process, from Eq. 1 is consumed to produce DME

methanol is synthesized first from synthesis gas and water as in Eq. (2). Water produced is
using a metallic catalyst and then is dehydrated consumed by water gas shift (Eq. 3) and
on acid catalyst to form DME [3]. Direct dimethyl produces carbon dioxide.
ether synthesis from synthesis gas can be As seen from Eq. 1 2 and 3 DME
accomplished by using a bi-functional catalyst synthesis is highly exothermic. An exothermic
which is the combination of methanol synthesis reaction requires thermodynamically low
and methanol dehydration catalysts. Three reaction temperature, while higher reaction
reactions are involved in the direct DME synthesis rate requires higher reaction temperature thus
process using carbon monoxide and hydrogen there is an optimum temperature in direct
as feed reactants: DME synthesis. Moreover, with mole reduction
reactions, increasing pressure increases
Methanol synthesis reaction: synthesis gas conversion. However, a high
CO + 2H2 CH3OH (1) pressure system has high capital and
Methanol dehydration reaction: operating costs and experimental results
2CH3OH CH3OCH3 + H2O (2) provide adequate information on cost
Water gas shift reaction: optimization. Reactor size also affects the
CO + H2O CO2 + H2 (3) optimum operating conditions. High space
velocity provides less gas-solid reaction time

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83 26 - 2556

and the synthesis gas conversion should be
lowered. Moreover, different types of reactors
have different optimum operating conditions
depending on the material balance of the different
flow patterns. Gas/solid contact behaviors are
usually plug-flow, mixed flow, or a combination
of both. The optimum temperature of reversible
exothermic reactions is found by conducting
experimental trials. In this study, experiments
with a packed bed reactor were conducted to
identify the optimum operating conditions such
as feed compositions, temperatures, pressures,
and space velocities.
with a ratio of 4:1, was prepared by the co-
Kinetic parameters for a particular
catalyst are important for development of DME
production at any scale. The kinetic parameters
are used in reactor design and scale-up. The
kinetic models of DME production rate are
complicated due to the multi-catalyst active
sites adsorption mechanisms. They are
bar pressure and temperature 245-275 C. The
usually a combination of three separate kinetic
reactions. Kinetic parameter estimation is
usually accomplished by performing experi-
ments in a lab scale reactor. The flow pattern
of the reactor combined with the kinetic model
provides kinetic parameters. Reactor flow,
either a plug flow or mixed flow depending on
the reactor type, can be identified.
was used for H2 and CO. Reactor performance
This work aims to develop kinetic
models for direct DME synthesis from synthesis
gas which include three consecutive reaction
mechanisms (Eq. 1 2 and 3) and all species
66
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involved are accounted for in the proposed
kinetic model. The kinetic parameters are
estimated from the observed experimental
results.
Methodology
Experiments and parameters estimation
were carried out as follows:
1.1 Experimental Runs
The catalyst, CuO-ZnO-Al2O3:HZSM-5
precipitation method. Before each reaction, the
catalyst was activated by reduction with pure
hydrogen at 230 C and atmospheric pressure.
The conversion of synthesis gas to DME was
studied under a continuous feed and steady-
state condition in a fixed-bed reactor at 20-50
effluent was kept at a temperature over 100 C
to avoid condensation of water and methanol.
The product gases were analyzed by a Shimadzu
8A gas chromatograph (GC), with a thermal
conductivity detector (TCD). Porapak Q column
was used for DME, methanol, water, and CO
analysis while a molecular sieve 5A column
was reported in terms of total CO conversion
and product selectivity, which are expressed
as:
Total CO conversion (XCO)
constant (K eq1, K eq2 and K eq3). The resistance


total gram atoms of C converted or adsorption term was developed and the
= (5)

gram atoms of C in feed
parameters included are KCO, KH2, KM, KW, and

Kco2. The proposed model is based on reaction
Product selectivity (S)
mechanisms. The reactions take place on the
gram atoms of C converted to product active site of the catalyst surface. Molecules
= (6)

total gram atoms converted
adsorb on the surface then react and the
product is desorbed. In this postulate, all
1.2 Parameter Estimation
components except DME adsorbed on the
The general rate expressions derived catalyst surface and hydrogen dissociatively
from various postulated mechanisms are all of adsorbs. Thus the model is expressed as:

the form [9]:


Methanol synthesis reaction:

Rate of reaction =




driving force of
(11)

(kinetic term) x
displacement from equilibrium


(adsorption term) (7)
Methanol dehydration reaction:



Thus the rates of the three reactions (12)

of direct dimethyl ether synthesis are arranged

into
Water gas shift reaction:




r1 = k1 x [driving force]1 / [adsorption]1 (8)
(13)

r2 = k2 x [driving force]2 / [adsorption]2 (9)


r3 = k3 x [driving force]3 / [adsorption]3 (10)
The reaction rate equilibrium constants

at temperatures of 200-300 C were calculated
The subscripts 1 2 and 3 are for from the ASPEN data base and are expressed
methanol synthesis, methanol dehydration, and in terms of temperatures as follows:

water gas shift reaction, respectively. The

driving force term includes the reaction rate (14)

order of each component. In addition, it is

related to the thermodynamic equilibrium

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83 26 - 2556
 The coefficients in Eq. 14 for the Therefore, the rate Equations (11)-(13)
calculation of thermodynamic equilibrium of
are expressed in dimensionless form as:
the three reactions are shown in Table 1.
(18)

Table 1 Coefficients of Equation 14 for the
(19)
calculation of thermodynamic equilibrium of

the three reactions
(20)
A B C D
Keq1 - 28.8 11,812.3 5.20 x 10 -3
-1.0701 x 10 -5
where the dimensionless kinetic
Keq2 - 2.27 2,609.5 8.23 x 10 -3
-8.2433 x 10 -6
parameters are defined as:
Keq3 - 4.68 4,764.8 13.351 x 10 -1.4258 x 10
-3 -5

Note: (21)
Keq1: CO hydrogenation: CO+2H2 CH3OH (1)
Keq2: Methanol dehydration: 2CH3OH CH3OCH3+H2O (2)
Keq3: Water gas shift reaction: CO+H2O CO2+H2 (3) (22)

The kinetic correlations were sub- (23)
stituted in a plug flow model, where the overall
material balance is: Non-linear regression with least square
method coupled with nonlinear ordinary dif-
(15) ferential equation solver was used to estimate
kinetic parameters from experimental results.
For each species, Eq. (15) becomes: Ordinary differential equation solver was used
to calculate the reactor performance from the
(16) developed kinetic correlations and the results
were compared with experimental data.
Let and, then a dimensionless mole
change expression for each species can be Results and Discussions
expressed as:
This study focuses on three parts
(17) including experimental results, kinetic
parameter estimation and a comparison of
calculation and experimental results.
68
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 1.3 Experimental results synthesis gas conversion decreased. An
Figures 1 and 2 show CO conversions exothermic reaction requires thermodynamically
at pressures of 20-50 bars and temperatures of low reaction temperature, while the reaction
245-275 C. A wide range of space velocities rate requires high reaction temperature. Thus
was investigated (1,958-23,099 ml/g cat-h
by increasing the temperature to increase CO
STD). CO conversion changes with increasing conversion for dimethyl ether synthesis, there
pressure, temperature and space velocity. For is a thermodynamic equilibrium limitation. The
pressure of 20-50 bars, the results showed decrease in CO conversion at 275 C shows

higher CO conversion at higher pressure. the thermodynamic limitation of the system.
Similar experimental findings were obtained
From Figures 1 and 2, CO conversion
by Jia et al, 2002, Lu et al., 2004, and Erea
decreased gradually with the increase in space
et al., 2005 [1 3 and 4]. The overall direct velocity and kept almost unchanged at the
dimethyl ether synthesis, Reaction (4), exhibits higher space velocity, especially beyond 8,000
great mole reduction from 6 to 4 moles, thus ml/gcat-h. Space velocity is defined as the
while reaction occurred the pressure decreased. volumetric flow rate of synthesis gas per gram
In order to reach equilibrium, the system will of catalyst. Thus high space velocity indicates
convert the reactants into products to increase less gas-solid reaction time and results in lower
the number of moles on the product side. As a conversion. At space velocities above 8,000 ml/
result, increasing pressure will increase the gcat-h, the reaction is limited by the amount

total conversion of the system (Le Chateliers of catalyst. As a result, low and unchanged
Principle). Consistent with this, the highest CO
conversion observed from the experimental
runs over a wide range of pressures, 20-50
bars, was 64% at 50 bars.
In order to identify the temperature
effect of direct DME synthesis, experimental
runs were conducted under constant pressure
of 30 bars with various temperatures in the
range 245-275 C. CO conversion increased with
increasing temperature from 245-265 C and the Figure 1 : Experimental results of CO
highest CO conversion observed was 53% at conversion in direct DME synthesis at constant
265 C. At the higher temperature of 275 C, temperature

69
83 26 - 2556
conversion was observed. However, at higher The kinetic parameter was also obtained
pressure, the velocity limited is higher because as follows:
the reaction is more favorable with increasing
pressure. k1 = 260.2e(-57,887/RT) (25)

k2 = 1.69x106e(-69,782/RT) (26)

k3 = 12.07e(-20,452/RT) (27)

The above parameters in the correlations
indicate that the adsorption rate constants of
carbon monoxide and carbon dioxide are very
low compared to those of hydrogen, methanol,
Figure 2 : Experimental results of CO and water, thus the adsorption effect of those
conversion in direct DME synthesis at constant reactions are minor. Also, the kinetic rate
pressure constant of methanol synthesis is the lowest
compared to those of methanol dehydration
1.4 Kinetic Parameter Estimation and water gas shift reaction, thus the methanol
Results synthesis reaction is expected to be the rate
Data fitting was carried out by nonlinear determining step.
least squares regression. The estimated adsorption
constants are: 1.5 Comparisons of Calculations
and Experimental Results
KCO = 3.60x10-7e(60,532/RT),(bar-1) (20) The kinetic model was used for
calculations and the results were compared
KCO2 = 8.73x10-8e(66,932/RT),(bar-1) (21) with experimental results. The parity plot
results are shown in Figure 3 and CO conver-
KH2 = 0.20e(30,963/RT),(bar-1) (23) sion, product selectivity, and product molar
fraction of calculation and experimental results
KM = 0.77e(16,244/RT),(bar-1) (23) are compared in Figures 4 and 5. The calculation
results agree with the experimental results
KW = 5.54e(26,454/RT),(bar-1) (24) within, except for a few points at a tempera-

70
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ture of 275 C (Fig. 4). This condition is in the
range of thermodynamic equilibrium limitation
of exothermic reaction which the sharp break
of the experimental data is obtained.
minimum CO2 byproduct [10].
The kinetic model calculated and
experimental results exhibit increasing CO
conversion with increasing pressure and
temperature. At a temperature of 275 C ,
approximately 66% and 33%, while methanol
the calculated conversion is higher than
experimental results thus different optimum
temperature is observed. The thermodynamic
equilibrium limitation of exothermic reaction
was calculated to be at 280 C (Fig. 4).
dioxide.
Both calculated and experimental
results indicated that most end products are
DME and carbon dioxide with low methanol
content as shown in Figure 5. The results
indicate that the reaction occurs according to
Eq. 4. Low methanol and high carbon dioxide
products were observed, thus methanol
produced from CO hydrogenation is consumed
instantly to produce DME. Water is consumed
by water gas shift reaction and produced
carbon dioxide. Although water removed by
water gas shift reaction prevents catalyst
deactivation from the hydrophobic behavior of
HZSM-5, the carbon dioxide produced is a
greenhouse gas. As a result, the carbon dioxide
by-product is usually recycled back into
kinetic models were developed and the
the system through a reformer. An efficient
83 26 - 2556
reformer can provide carbon monoxide and
hydrogen from carbon dioxide, oxygen, and
methane at the optimum ratio of 1 with
Figure 5 also shows that pressure
and temperature have no effects on product
selectivity. DME and CO 2 selectivities are
selectivity is very low. Almost all methanol
produced in the system was converted to
DME and water produced from methanol
dehydration, Eq. 2, was converted to carbon
Conclusion
Performance of direct dimethyl ether
synthesis in a fixed bed reactor over a bi-
functional catalyst, CuO-ZnO-Al2O3/HZSM-5,
was studied. CO conversion increased with
increasing pressure (20-50 bars). CO conversion
increased with increasing temperature over the
range 245-265 C and then decreased as the
temperature increased to 275 C. The maximum
was due to thermodynamic equilibrium limitation
of the exothermic reaction. In addition, the
conversion increased with decreasing space
velocity due to increased reaction time. The
correlations agree well with experimental data.
71
 (a) CO conversion
(b) DME molar fraction (c) CO2 molar fraction

(d) Methanol molar fraction (e) Water molar fraction

Figure 3 Parity diagrams for CO conversion (a), and product distribution in terms of product molar
fractions of DME, carbon dioxide, methanol, and water (be, respectively)

Figure 4 Effects of temperature and pressure on CO conversion of dimethyl ether systhesis from
experiments and calculation

72
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Figure 5 Effects of temperature and pressure on product selectivity and product distribution of
dimethyl ether systhesis from experiments and calculation.

Notation

k j Kinetic rate constant of reaction j yi molar fraction of specie i
k*j Dimensionless kinetic rate constant of
Space-time (g/mol/sec)
reaction j Wcat Catalyst weight (g)
Ki Adsorption constant of specie i R Universal gas constant (J/mol K)
Keq j Equilibrium constant of reaction j
R j Rate of reaction j Acknowledgements
r ij Rate of specie i in reaction j
r*j Dimensionless rate of reaction j This research was carried out with the
ij Stoichiometry of specie i in reaction j financial support of the Kasetsart University
T Temperature (K) Research Development Institute, the Center

pi Partial pressure of specie i (bar) for Excellence in Petroleum, Petrochemicals,

PT Total pressure (bar) and Advanced Materials, S&T Postgraduate
FT Molar flow rate (mol/sec) Education Research Development Office, and
Fi Molar flow rate of specie i the KU Faculty of Engineering.

73
83 26 - 2556

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