TSINGHUA SCIENCE AND TECHNOLOGY

ISSN 1007-0214 07/20 pp168-176

Volume 9, Number 2, April 2004

Thermodynamics of the Single-Step Synthesis of

Dimethyl Ether from Syngas

WANG Zhiliang (ฆᄝ॥), WANG Jinfu (ฆࠡ‫**)׾‬, REN Fei (ఉ ‫)׆‬,

HAN Minghan (‫ۂ‬ੜ‫)ۑ‬, JIN Yong (ࠡ င)

Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Abstract: A detailed thermodynamic analysis of single-step synthesis of dimethyl ether (DME) from syngas
has been performed. From experiments and theoretical calculations, a suitable thermodynamic model based
on Reid’s thermodynamic data and the Soave-Redlich-Kwong equation of state was determined. Using this
model, a careful analysis of direct synthesis of dimethyl ether from syngas was carried out. Reaction syn-
ergy in the synthesis can greatly improve CO conversion and DME yield. Lower temperatures and higher
pressures favor higher CO conversion and DME yield. Compared to methanol synthesis, however, the tem-
perature has a smaller effect on the reaction. The direct synthesis of dimethyl ether can exploit CO-rich
syngas efficiently due to the maximum DME yield obtained at H2/(CO+CO2) mole ratio =1. A small amount
of CO2 in the reactant mixture has little effect on the reaction. Under conditions of H2/(CO+CO2) feedstock,
water in the system can improve the reaction performance.

Key words: dimethyl ether; methanol; syngas; chemical equilibrium

Introduction traditional diesel fuel can be achieved, but with much

lower NOx emission, smokeless combustion and less en-
Dimethyl ether (DME) is a useful building block for gine noise. The emission levels are below the strict crite-
producing important chemicals such as dimethyl sulfate ria prescribed by the California Ultra-Low Emissions
and high-value oxygenated compounds. DME is also Vehicle (ULEV) Standard.
used as an aerosol propellant in many products including Direct synthesis of DME from synthesis gas is also
hair spray, perfumes and shaving cream, as a conse- called DME synthesis in a single step. In a single reactor,
quence of its more environmentally-benign properties methanol synthesis (1) and methanol dehydration (3)
compared to other propellants[1, 2]. Furthermore, DME has proceed over a dual catalyst simultaneously. Methanol is
drawn more attention as an alternative clean fuel for the transformed into DME after it is produced by reaction (1).
diesel engine[3,4]. DME has excellent behavior in com- As a result, higher equilibrium conversions can be
pression ignition combustion, possessing a cetane number obtained as compared to methanol synthesis alone. Due
of over 55, and zero sulfur content. Engine tests carried to the synergy effect, the single-step production cost of
out by Amoco and Haldor Topsoe amongst others have DME is much lower than the cost of its production from
indicated that with minor fuel system modification, en- syngas in a two-step process.
gine operation with a thermal efficiency equivalent to
Methanol synthesis:
Received: 2002-12-04; revised: 2003-07-11 CO+2H2 CH3OH ˉ90.4 kJ/mol (1)
γγTo whom correspondence should be addressed. Water gas shift reaction:
E-mail: wangjf@flotu.org; CO+H2O CO2+H2 ˉ41.0 kJ/mol (2)
Tel: 86-10-62785464 Methanol dehydration:
 WANG Zhiliang (ฆᄝ॥) et alġThermodynamics of the Single-Step Synthesis of ĂĂ 169

2CH3OH CH3OCH3+H2O ˉ23.0 kJ/mol (3) Q A 'G 0f ,A,298.15K  Q B 'G 0f ,B,298.15K (8)
In this paper, a thermodynamic equilibrium model that The ideal gas heat of reaction or the standard reaction
can predict thermodynamic behavior in the direct heat can be calculated from the isobaric heat capacities:
synthesis of DME from syngas and that can provide T
'H R0  'H R,298.15K
0 0
³298.15K 'C p dT (9)
reliable basic data for simulations and engineering
0
applications was developed using experiments and in which 'H R,298.15K is the standard reaction heat at
theoretical calculations. The effect of reaction 298.15 K, i.e., represents the difference between the
temperature, pressure, mole ratio of H2/(CO+CO2), CO2 standard formation heats 'H 0f ,298.15K of products and re-
content, and water content in the reactant mixture has
been investigated. actants at 298.15 K.
0
'H R,298.15K Q L 'H 0f ,L,298.15K  Q M 'H 0f ,M,298.15K 
1 Calculation of Chemical
Q A 'H 0f ,A,298.15K  Q B 'H 0f ,B,298.15K (10)
Equilibrium Constants
If relevant data for the related physical properties are
1.1 Calculation of ideal chemical equilibrium known, the equilibrium constant Kf can be calculated
constants
theoretically. In Eq. (9), the isobaric heat capacities C 0p
Reactions (1)-(3) can be written in the following form: at various temperatures can be obtained from empirical
vA A  vB B œ vL L  vM M (4) correlations. The following expressions are used:
in which A and B represent reactants, and L and M rep- C 0pi /(J mol1 K 1 ) A0i  A1i (T / K)  A2i (T / K)2 
resent products. vA, vB, vL, and vM are the corresponding
A3i (T / K)3  A4i (T / K) 4 (11)
stoichiometric coefficients. At the constant pressure, the
1 1
relationship between the equilibrium constant and tem- C 0pi /(J mol K ) A0i  A1i (T / K) 
perature is given for an ideal gas by the Van Hoff A2i (T / K) 2  A3i (T / K)3 (12)
equation:
C 0pi /(J mol1 K 1 ) A0i 
§ w ln K f · 'H R0
¨ ¸ (5) 2
© wT ¹ p RT
2 ª§ A · § A ·º
A1i «¨ 2i ¸ sinh ¨ 2i ¸ » 
where R is the ideal gas constant. By integrating Eq. (5), ¬© T / K ¹ © T / K ¹¼
2
we obtain ª§ A · § A ·º
A3i «¨ 4i ¸ cosh ¨ 4i ¸ » (13)
¬© T / K ¹ © T / K ¹¼
ln K f
³ln K f ,298.15k d ln K f ln K f  ln K f ,298.15K
The values of the related coefficients can be readily
T 'H R0
³298.15K
dT (6) obtained from Refs. [5-7].
RT 2
In addition to theoretical calculations using the stan-
'G 0f ,298.15K dard reaction heat and isobaric heat capacities, many em-
where ln K f ,298.15K  (7)
298.15 R pirical correlations have also been developed through
'G 0f ,298.15K Q L 'G 0f ,L,298.15K  Q M 'G 0f ,M,298.15K  experimental study. Some of these empirical correlations
are summarized in Tables 1-3.

Table 1 Empirical correlations for the chemical equilibrium constant of methanol synthesis

Empirical correlations References

ª 9143.6 º
K fCO 9.740 u 105 u exp « 21.225   7.492ln(T / K)  4.076 u 103 T / K  7.161u 108 (T / K)2 »   [8]
¬ T /K ¼
3921
lg K fCO 10.20   7.971lg(T / K)  2.499 u 103 (T / K)  2.593 u 107 (T / K) 2 [9]
T /K
3981
lg K fCO 8.729   7.411lg(T / K)  2.403 u 103 T / K  2.15 u 107 (T / K) 2 [9]
T /K
 170 Tsinghua Science and Technology , April 2004, 9(2): 168̢176

(Continuted)
Empirical correlations References
3748.7
lg K fCO 13.8144   9.2833lg(T / K)  3.1475 u 103T / K  4.2613 u 107 (T / K)2 [5]
T /K
5139 § 98 475 ·
lg K fCO  12.621, K fCO 2.52 u 1013 u exp ¨ 1 ¸ [10], [11]
T /K © RT /(J mol ) ¹
16 251.2
lg K fCO 28.18   7.97ln(1.8T / K)  0.0032 u 1.8T / K  2.1 u 107 (1.8T / K)2 [12]
1.8T / K

Table 2 Empirical correlations for the chemical equilibrium constant of water gas shift (WGS)

Empirical correlations References

ª 5639.5 49 170 º
K f WGS exp «13.148   1.077ln(T / K)  5.44 u 104 T / K  1.125 u 107 (T / K) 2  » [13]
¬ T / K (T / K) 2 ¼
4578 2167
ln K f WGS 4.33  , lg K f WGS 1.2777   0.5194lg(T / K)  1.037 u 103 T / K  2.331 u 10 7 (T / K) 2 [9,5]
T /K T /K
2167
lg K f WGS 1.2777   0.5194lg(T / K)  1.037 u 103 T / K  2.331 u 107 (T / K) 2 [5]
T /K
2073 8240 4578
lg K f WGS   2.029 , ln K fWGS 4.33  , ln K f WGS 4.33  [10,12,9]
T /K 1.8T / K T /K
2167
lg K f WGS 1.2777   0.5194lg(T / K)  1.037 u 103 T / K  2.331 u 107 (T / K) 2 [5]
T /K

Table 3 Empirical correlations for the chemical equilibrium constants of methanol dehydration

Empirical correlations References

4019
ln K fDME 26.64   3.707ln(T / K)  2.783 u 103 T/K + 3.8 u 10-7 (T / K) 2  6.561 u 104 /(T / K) 2  26.64 [14]
T /K
2835.2
ln K fDME 13.36   1.68ln(T / K)  2.4 u 103 T / K  2.1 u 107 (T / K)2 [12]
T /K

The equilibrium constants can be obtained either from

thermodynamic formulae or from empirical expressions.
In this paper, different methods including three methods
derived from different heat capacity correlations and em-
pirical correlations are compared. Systematic simulations
have been performed in the temperature range of 493-553
K. The results are shown in Figs. 1-3.
It can be seen that considerable difference exists be-
tween the values obtained from each of the different
methods. Some methods can even yield values that are
Fig. 1 Chemical equilibrium constants of methanol
only half of those from other methods. The relationships
synthesis
between the thermodynamic data and chemical equilib-
rium constants are logarithmic, so slight differences in 1.2 Equilibrium constant under non-ideal gas
thermodynamic data used by different methods can result conditions
in large disparities. From these data, we conclude that it is
necessary to carry out an experimental study to test and In addition to the ideal gas equilibrium constant Kf , the
fugacities of the components must also be known in order
screen the existing methods.
 WANG Zhiliang (ฆᄝ॥) et alġThermodynamics of the Single-Step Synthesis of ĂĂ 171

pL pM
( )Q L ( )Q M
ILvL IMvM pq pq
Kf
IA IB ( pA )Q A ( pB )Q B
vA vB

pq pq
P Q L Q M Q A Q B ILvL IMvM yLvL yM
vM
( ) KI K p (15)
pq IAvA IBvB yAvA yBvB
The fugacity coefficients in the above two formulae
can be obtained from the following equation together
Fig. 2 Chemical equilibrium constants of water gas shift with the gas equation of state.
ª º
1 V « RT § wp · »dV  ln Z
ln Ii ³  ¨ ¸ (16)
RT f « V © wni ¹T ,V ,n »
¬ j ¼

The Peng-Robinson (P-R) equation[15] or the

Soave-Redlich-Kwong (SRK) equation[16] is commonly
used for calculating the fugacity coefficients of the com-
ponents in the methanol synthesis system. The P-R and
SRK equations have been used to calculate the equilib-
rium composition of a reaction system at 523 K and 6.0
MPa. The initial composition of the syngas was taken as
Fig. 3 Chemical equilibrium constants of methanol nH2ĩnCOĩnCO2=0.6667ĩ0.3200ĩ0.0133. The thermo-
dehydration
dynamic data are from Reid[17]. The results are shown in
to calculate the equilibrium composition. For component Table 4. It is seen that the P-R equation and the SRK
i, the fugacity fi is the product of its partial pressure pi and equation yield almost identical results for calculations for
the fugacity coefficient Ii , i.e., the DME synthesis system. In this paper, the SRK equa-
fi piIi PyiIi (14) tion is used.
Thus, Kf can be expressed as
Table 4 Comparison of calculations based on the P-R equation and the SRK equation

yH 2 yCO yCO2 yH 2 O yCH3OH yCH3OCH3

P-R equation 0.2634 0.0077 0.0871 0.0364 0.0183 0.1101
SRK equation 0.2701 0.0085 0.0889 0.0340 0.0169 0.1095

2 Determination of Thermodynamic
Model
2.1 Experimental setup
Figure 4 shows a schematic diagram of the experimental
system. CO (containing a small amount of CO2) and H2
are supplied from gas bombs. After passage through
pressure regulators and mass flow controllers, the two
gases are mixed. The mixture is preheated to the reaction
temperature before entering the reactor. There is a
high-pressure gas-liquid separator at the exit of the reac-
tor. The gas phase flows through a back-pressure regula-
tor and is analyzed on-line by gas chromatography. The
flow rate is measured with a wet-flow meter. The liquid
phase flows through a needle valve and enters a nor-
mal-pressure gas-liquid separator. The liquid product
(methanol) is weighed. The composition of the gas re-
leased from the liquid is also analyzed by gas chroma-
tography and its flow rate is measured with another
wet-flow meter.
The reactor is an isothermal fixed-bed reactor with a
diameter of 15 mm and a length of 1100 mm. Five
thermocouples (‡ 0.5 mmh90 mm) are fixed at the two
ends, and to the upper, middle and lower parts of the re-
actor, to control and display the temperature in the reactor.
The temperature in the reactor is controlled by an
XMT-400 type intelligent temperature controller, pro-
duced by Beijing Chaoyang Automation and Instrument
Factory. The flow rates of H2 and CO are measured and
 172 Tsinghua Science and Technology , April 2004, 9(2): 168̢176

Fig. 4 Schematic diagram of the experimental setup

1, Carbon monoxide; 2, Nitrogen; 3, Hydrogen; 4, Pressure reducing regulator;
5, Mass flow controller; 6, Filter; 7, Check valve; 8, Preheater;
9, Pressure gauge; 10, Reactor; 11, Heating block; 12, Separator;
13, Back pressure regulator; 14, Needle valve; 15, Gas chromatograph;
16, Expansion vessel; 17, Wet-flow meter.

controlled by D08-2B type mass flow controllers manu- Systematic calculations have been performed based on
factured by Beijing Jianzhong Machine Factory. the previously mentioned methods. The results have then
A C301 commercial catalyst was used in the experi- been compared with experimental data. A model using
ment. The catalyst charge was 88.0 g. The catalyst was Reid’s thermodynamic data and the SRK equation gives
reduced with a mixture of H2 (3.4%) and N2 (96.6%) un- the best agreement between theoretical and experimental
der 0.1 MPa. The flowrate of the reducing gas was 50 results. The performance of this model is shown in Fig. 6
mL/min. Gases used in the experiment were: H2 (99.9%), and Fig. 7. Therefore, this model is chosen for use in the
CO (95.8%CO + 4.2%CO2), N2 (99.999%), He (carrying calculations of DME synthesis.
gas in gas chromatograph, 99.995%).
The influence of syngas space velocity on CO conver-
sion at 528 K and 6 MPa has been studied in the reactor.
The composition of the syngas was nH2  nCO  CO2 = 2.12.
The results are shown in Fig. 5. When the space velocity
of the syngas is less than 600 mL/ (g-cat·h), the syngas
conversion no longer decreases with decreasing syngas
space velocity, indicating that the exit gas mixture has
reached thermodynamic equilibrium. This observation
provides the basis for choosing the operational conditions
in the thermodynamic study. Fig. 6 Effect of temperature on equilibrium

Fig. 5 Effect of space velocity on reaction Fig. 7 Effect of pressure on equilibrium

 WANG Zhiliang (ฆᄝ॥) et alġThermodynamics of the Single-Step Synthesis of ĂĂ
3 Thermodynamic Analysis of the
Direct Synthesis of DME
By using the optimum thermodynamic model for calcula-
tion of the reaction equilibrium, the effects of reaction
temperature, pressure, mole ratio of H2/(CO+CO2), car-
bon dioxide content and water content in the reactant
mixture have been investigated.
3.1 Effect of temperature on reaction
equilibrium
The effect of temperature on the reaction equilibrium has
been calculated for a pressure of 5 MPa, nH2 / nCO+CO2 =
2.0 (nCO nCO2= 0.96 0.04). The results are shown in
Fig. 8 and Fig. 9.
Fig. 8 Effect of temperature on equilibrium conversion
It can be seen in Fig. 8 that the conversion of CO and
H2 in both DME synthesis and methanol synthesis de-
creases monotonically with an increase of temperature.
This behavior is consistent with the exothermicity of the
reaction. It is evident that CO conversion has been
sharply increased by the reaction synergy, whereas the H2
conversion does not increase, and actually decreases, due
to H2 production by water gas shift.
Fig. 9 Effect of temperature on equilibrium yield
173
From Fig. 9, it can be seen that with an increase of
temperature, the equilibrium yield of DME and the total
yield of methanol and ether during direct synthesis of
DME show a monotonic decrease, which is also consis-
tent with the exothermicity of the reaction. Due to reac-
tion synergy, the total yields of methanol and ether are
also higher than for the synthesis of methanol. Moreover,
the difference between the total methanol and ether yields
for direct synthesis of DME and the methanol yield for
methanol synthesis sharply increases with increasing
temperature. This is because the amount of heat released
by methanol synthesis is greater than the amount of heat
released in methanol dehydration. Although the increase
of temperature does not benefit either of these two reac-
tions, methanol synthesis is more affected. Accordingly,
due to the reaction synergy, the effect of temperature on
total yield of methanol and ether is lower than for
methanol synthesis.
3.2 Effect of pressure on reaction equilibrium
The calculated results of the effects of pressure on the re-
action at 523 K, nH2nCO+CO2=2.0 are shown in Fig. 10
and Fig. 11.
Fig. 10 Effect of pressure on equilibrium conversion
Fig. 11 Effect of pressure on equilibrium yield
 174
From Figs. 10 and 11, it can be seen that CO
conversion, DME yield, and total yield of methanol and
ether all increase monotonically with an increase in
pressure. It also can be seen that due to reaction synergy,
the total yield of methanol and ether is also higher than
for methanol synthesis. Differences between total yields
in DME synthesis and methanol synthesis decrease
rapidly, because methanol synthesis is a volume reducing
reaction but methanol dehydration is a constant volume
reaction. Accordingly, a higher pressure favors methanol
synthesis but does not have much effect on methanol
dehydration. On the whole, a high pressure favors total
reactions, but this effect is lower than in methanol
synthesis.
3.3 Effect of H2/(CO+CO2) mole ratio on reaction
equilibrium
The effects of H2/(CO+CO2) on the reaction at 523 K,
and 5.0 MPa are shown in Fig. 12 and Fig. 13.
Fig.12 Effect of H2/(CO+CO2) mole ratio on equilibrium
conversion
Fig. 13 Effect of H2/(CO+CO2) mole ratio on
equilibrium productivity
Figure 12 shows that with an increase in the H2 content
of the reactants CO conversion in both methanol and
DME synthesis increases whilst H2 conversion decreases.
Tsinghua Science and Technology , April 2004, 9(2): 168̢176
An increase in the proportion of H2 in the reactant mix-
ture favors CO conversion, which is the opposite of the
case for the water gas shift reaction. The reaction order
for the methanol synthesis reaction is 2, whilst for water
gas shift the reaction order is 1. An increase of H2 con-
version in the reactant mixture will therefore greatly fa-
vor the total reactions. In the synthesis of DME, if the H2
fraction is low, CO conversion increases rapidly, and at a
certain value, CO conversion approaches 98.0%. In
methanol synthesis, however, CO conversion continu-
ously increases with increasing H2 content.
Although an increase in H2 favors more CO conver-
sion, this does not mean that increased H2 also favors
equilibrium productivity. The calculated results for
methanol equivalent productivity of DME and methanol
synthesis versus nH2nCO+CO2 are shown in Fig. 13.
The maximum production of methanol is obtained at
nH2nCO+CO2= 2, which is the stoichiometric mixture in
methanol synthesis, Fig. 13. However, in DME synthesis,
the maximum of CO conversion, DME yield and total
yield of methanol and DME appear at nH2nCO+CO2= 1.
Therefore, the thermodynamic calculations indicate that
CO-rich synthesis gas as the feedstock in DME will give
higher total yields of methanol and DME.
3.4 Effect of the proportion of CO2 in the reactant
mixture on reaction equilibrium
It have been reported that appropriate content of CO2 in
the reactant mixture in methanol synthesis can improve
the activity of the catalyst, though too much CO2 will
prevent CO hydrogenation as a result of the strong ad-
sorption of CO2 on the catalyst surface. However, when
using a reactant without CO2, CO2 produced in the reac-
tions does not have much effect on CO conversion. It is
interesting to note that a small quantity of CO2 added to
the reactant mixture decreases the CO conversion but
slightly increases the DME selectivity[17].
One probable reason for this observation is that CO2
helps to maintain the Cu-based catalyst in a reduced state.
Although there is no consensus on the role of CO2 in the
hydrogenation of CO, it is generally accepted that a cer-
tain amount of CO2 in the reactant will increase the activ-
ity of the catalyst. The effect of CO2 on the reaction has
also been investigated in the present study. Figure 14
shows the effect of CO2 content at 250ć, 5.0 MPa,
nH2nCO+CO2=1.
 WANG Zhiliang (ฆᄝ॥) et alġThermodynamics of the Single-Step Synthesis of ĂĂ
Fig. 14 Effect of CO2 on reaction
Figure 14 shows that the conversion of CO and H2 de-
creased only slightly with increasing CO2 content. The
conversion of CO and H2, the yield of DME and the total
yield of methanol and DME all show little change. The
thermodynamic study indicates that a reactant mixture
with a certain amount of CO2 has only a slight effect on
reaction. Accordingly, CO2 can be included in the reac-
tant in the same manner as an inert gas. CO2 has a high
heat capacity, and can be used to regulate the temperature
of the bed and to improve the stability of the catalyst. In
addition, a certain amount of CO2 can prevent the water
gas shift reaction and improve the DME selectivity.
3.5 Effect of H2O
Effect of H2O in the reactant mixture on the reaction at
523 K, 5.0 MPa, and two different values of nH2nCO+CO2
are shown in Fig. 15 and Fig. 16. The H2O content has a
large effect on the reaction for high H2/ (CO+CO2) mole
ratio reactant mixtures. With increased water in the reac-
tion system, the conversion of CO and H2 changes a great
deal, and the yield of DME and total yield of methanol
and DME decrease rapidly in the case of
nH2nCO+CO2=21. Water has little effect on the reaction
when the nH2nCO+CO2 is 1:2. The total yield of methanol
and DME has a maximum value at a certain amount of
water content.
Fig. 15 Effect of H2O in reactant on conversion
175
Fig. 16 Effect of H2O in the reactant mixture
on productivity
With a reaction feedstock of high H2/(CO+CO2) mole
ratio, a large amount of water will be produced because
in the presence of a high concentration of hydrogen, wa-
ter gas shift in the forward direction to remove the water
is not thermodynamically favorable. Methanol dehydra-
tion will therefore become the reaction bottleneck. If a
reactant mixture with a high H2/(CO+CO2) mole ratio is
used, water produced in the reactions should be removed
by some other means. In present case, water removal can
result in a high DME yield and a high total yield of
methanol and DME. However, water has little effect on
the reaction for the case of reactant mixtures with low
H2/(CO+CO2) mole ratio because with CO-rich feed-
stocks, the water gas shift reaction in the forward direc-
tion is thermodynamically favorable, and water is re-
moved from the reaction system efficiently. Accordingly,
the direct synthesis of DME from syngas can use CO-rich
feedstocks and obtain better reaction results. For reaction
mixtures with a high content of CO, the optimum
nH2nCO+CO2can be regulated by introducing the required
amount of water vapor.
4 Conclusions
Various methods of calculating the equilibrium constants
for the direct synthesis of DME are compared, and a sys-
tematic experimental study of the thermodynamics of
methanol synthesis has been carried out in a fixed-bed
reactor. A thermodynamic equilibrium model using
Reid’s thermodynamic data and the SRK equation gives
results that agree well with the experimental data. From
an analysis of the thermodynamic trends in the direct
synthesis of DME, the following conclusions can be
drawn:
1) Reaction synergy in the direct synthesis of DME can
greatly improve CO conversion, the DME yield and the
 176 Tsinghua Science and Technology , April 2004, 9(2): 168̢176

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