Chemical Engineering and Processing 46 (2007) 905–909

The characteristics of liquid-phase methanol synthesis

in an impinging stream reactor
Hu Lishun ∗ , Wang Xinjun, Li Xiaoming, Yu Guangsuo,
Wang Fuchen, Yu Zunhong
Institute of Clean Coal Technology, East China University of Science and Technology,
Shanghai 200237, China
Received 19 January 2007; received in revised form 17 April 2007; accepted 4 June 2007
Available online 17 June 2007

Abstract
A laboratory scale mini-pilot plant is successfully designed and built to carry out research in the liquid-phase methanol synthesis process in a
impinging stream reactor, the reactor has good heat transfer and mass transfer performance because the catalyst slurry is atomized into fine drop
when it goes through the pressure-flow nozzles, the mass transfer between gas phase and liquid-phase is promoted. Sustained operating conditions
of temperatures approximately at 230 ◦ C, space velocity at 10,000 h−1 , high slurry recirculation flow rate and two or four opposed nozzles represent
a major extension of the operating range for this type of reactor. A high slurry recirculation flow rate is benefit to the inter-phase mass transfer
because the inter-phase disturbance is enhanced, and the catalyst slurry after atomized impacts each other when the opposed nozzles are used, this
promotes the inter-phase interfusion and distribution so as to increase the gas–liquid mass transfer.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Liquid-phase methanol synthesis; Impinging stream reactor; Pressure-flow nozzle; Mass transfer

1. Introduction
The liquid-phase methanol (LPMeOHTM ) synthesis process
was first developed by Chem Systems Company in 1975, and
research has been taken over by Air Products and Chemicals. The
liquid-phase methanol synthesis process provides the advan-
tages of improved heat transfer efficiency, excellent control of
exothermic heat of reaction, better adaptability of CO-rich syn-
gas feed. Due to the reaction, is taken in a liquid medium, it offers
better utility of carrying out the reaction as well as conducting
heat removal, which offers superior heat management pertaining
to the synthesis gas conversion to methanol and thereby prolongs
catalyst life.
During last two decades, many reactor designs have been
proposed for liquid-phase methanol synthesis, such as slurry
reactor which was proposed in 1980s [1–5], liquid entrained
reactor which was proposed and researched in the early 1990s
∗ Corresponding author.
E-mail address: icct hu@126.com (L. Hu).
[6–9], trickle bed reactor which was investigated in 1990s mostly
[10–11]. However, in these reactors the presence of an inert
liquid, such as paraffin presents an additional resistance to mass
transfer in the LPMeOHTM process. Although hydrogenation
reaction rates are governed by specific factors, when the slurry
concentration is very high, it seems that the rate determining step
is the gas-to-liquid mass transfer step and this problem become
outstanding as higher activity catalyst proposed.
To overcome the problems with the high mass transfer resis-
tance in aforementioned reactors, impinging stream reactor is
proposed and used to liquid methanol synthesis. Impinging
streams offer an effective flow configuration for intensifying
heat and mass transfer processes between gas–solid, solid–liquid
and liquid–liquid systems. The flow vectors of the streams
are directed against each other so that the steams collide in
a narrow zone, where heat and mass transfer between the
streams become extremely high. Due to its high efficiency,
impinging streams have found many applications in the chem-
ical and food industry as alternatives to conventional unit
operations [12], mixers [13–15] and dryers [16–17], chemi-
cal reactors [18–20]. In recent years, impinging streams has

0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2007.06.001
906 L. Hu et al. / Chemical Engineering and Processing 46 (2007) 905–909
Table 1
The component and purity of raw gas
Gas Component
Hydrogen H2
CO
H2
Carbon monoxide O2
N2
H2 O
Carbon dioxide CO2
been widely used in water–coal slurry gasification process
[21–22].
A pressure-flow nozzle is also used in the reactor to atomize
the catalyst slurry into fine drop just several hundred microns,
so the interface between syngas and liquid is increased sharply,
and in this moment the intensive shearing action also has the
effect of reducing the resistance of mass transfer from the gas-
to-liquid phase. Due to this reason, it is expected that impinging
stream reactor will exhibit an increase in mass transfer rates and
hence an increase in the overall reaction rates compared to the
other liquid-phase methanol synthesis reactor.
Furthermore, in whatever agitated slurry reactor or bubble
slurry reactor the catalyst agglomerates is inevitable, while in
impinging stream reactor it will be broken when atomizing, and
the catalyst particles are uniformly suspended easier in the liquid
for the catalyst slurry recirculated, so the catalyst concentration
can reach higher than other slurry reactor.
2. Experimental procedure
The raw gas used, in this work, is from cylinder, the com-
ponent and purity of the raw gas is listed in the Table 1. The
pure H2 , CO and CO2 from the cylinder of a desired flow rate
Fig. 1. Schematic of the overall mini-pilot plant system.
goes through a mass flow controller (Sevenstar HuaChuang, D07
Series), then blends in a blender before flowing into reactor. The
Content pressure of the syngas entering the reactor is regulated by using
≥99.9%
a forward pressure regulator mounted at the exit of the cylinder.
A schematic of the overall mini-pilot plant system is shown in
≥99.8%
Fig. 1. The impinging stream reactor has two parts, the upside of
<100 ppm
<250 ppm the reactor is reaction part, where the syngas and catalyst slurry
<800 ppm contact and take reaction in this part, and the other is called
<30 ppm slurry part in which the catalyst slurry is loaded, these two parts
≥99.9% are separated by a conical plate with a 40 mm hole in the middle.
The details of the impinging stream reactor system are shown
in Fig. 2. An impinging stream reactor, which is made of stain-
less steel with 100 mm inner diameter and 1500 mm height of
reaction part, is used in this experiment. The reactor is rated for
a maximum allowable working pressure of 5.0 MPa at 330 ◦ C.
It is equipped with an electric heating device capable of rais-
ing the temperature of the slurry in the reactor to the operating
temperature.
The reactor has four dual-channels pressure-flow nozzles and
one product outlet line. The nozzles are set at the place 200 mm
away from the top of the reactor and all nozzles are put horizon-
tally at the same plane, the details of the pressure-flow nozzles
are shown in Fig. 3. The feed gas is introduced through the annu-
lus channel of the nozzle and the catalyst slurry goes through the
center channel. Five thermocouples (type K Chromel-Alumel)
are put from the top to the bottom of the reactor, respectively. All
thermocouples are connected to a temperature recorder, and the
third thermocouple from the top is connected to a proportional
temperature controller which regulates the power supply to the
electric heating device.
The slurry is recirculated in the impinging stream reactor
from slurry part to reaction part by a slurry pump which is a
plunger-type reciprocating pump. The maximum flow rate deliv-
ered by this pump is 400 L h−1 . A buffer is located at the outlet
of the pump to ensure the recirculated slurry flow continuous.
 L. Hu et al. / Chemical Engineering and Processing 46 (2007) 905–909
Fig. 2. Details of the impinging stream reactor.
The pressure in the impinging stream reactor is maintained
at a desired pressure by a backpressure valve. The unreacted
gases and product leave the reactor in a product line to the con-
denser, the products flow through the inner tube of the condenser,
while tap water flows through the outer tube. A sample bottle
is installed at the exit of the condenser. One valve is installed
before the sample bottle and another is installed after it to safely
withdraw the sample without disturbing the system.
Fig. 3. Details of the flow-pressure nozzle.
907
The flow rate of the vent gas is measured by a flow meter,
a valve, which is installed on this stream, allows the vent gas
either to be vented or to be collected by an air chamber and then
analyzed by a gas chromatograph each 30 min.
All the research discussed below is carried out with a com-
mercial Cu-based methanol synthesis catalyst (C307, Research
Institute of Nanjing Chemical Industry Group, China), the
details of the catalyst can be found in reference [23]. The liquid
used in the experiment is a type of liquid paraffin (Produced
by DaChang Plant, Shanghai, China), the detail property of this
paraffin has been reported in reference [24] and the catalyst is
reduced in situ under the operating conditions of space velocity
5000 h−1 , ratio of hydrogen and nitrogen is 5:95, the temperature
programming is the same as the reference [25].
3. Results and discussion
3.1. Effect of temperature
According to thermodynamic theory, the methanol synthesis
reaction is an exothermic reaction, a diminution of temperature
results in the equilibrium composition towards the formation of
MeOH carbonylation reaction, however, the hydrogenolysis rate
is too slow at low temperature. From the viewpoint of kinetics,
an increase in temperature favors the rate of a chemical reaction.
Therefore, it is a consequence of two competing effects stated
above that it has an optimal operating temperature range for
methanol synthesis.
For the operating conditions of a pressure of 3.8 MPa, a space
velocity of 10,000 h−1 , a H2 /CO/CO2 ratio of 70/25/5, a cata-
lyst concentration of 10% by mass, a recirculation flow rate
of 120 L h−1 , two opposed nozzles are used in the experiment.
Figs. 4 and 5 show that the effluent methanol concentration and
methanol productivity obtained in the impinging stream reactor
with the temperature rising.
3.2. Effect of space velocity
Space velocity is the ratio of gas flow rate to volume of cata-
lyst loaded. To the any catalytic reaction the space velocity has
greatly effective on the inter-phase mass transfer. As a rule, the
increasing of space velocity may reduce the liquid-phase diffu-
sion resistance remarkably. In the experiment less than 200 mesh
catalyst is used, so the internal diffusion in the catalyst can
be ignored, but the external diffusion may cause considerably
influence to the global rate of reaction.
Fig. 4. Effect of temperature on methanol productivity.
908 L. Hu et al. / Chemical Engineering and Processing 46 (2007) 905–909
Fig. 5. Effect of temperature on effluent methanol concentration.
Fig. 6. Effect of space velocity on methanol productivity.
For the operating conditions of 3.8 MPa, a temperature of
220 ◦ C, a H2 /CO/CO2 ratio of 70/25/5, a recirculation flow rate
of 120 L h−1 and two opposed nozzles are used in the experi-
ment. Figs. 6 and 7 show the result of the methanol productivity
and effluent methanol concentration with improving the space
velocity under catalyst concentration of 4 and 10% by mass,
respectively.
The shape of the curve in Fig. 6 increases almost con-
stantly before the space velocity attaining 10,000 h−1 , and after
10,000 h−1 the curve remains a certain value. This tends imply
that the reaction may be limited by the external diffusion before
space velocity of 10,000 h−1 , but the inter-phase mass trans-
fer has less effect on the global rate of reaction after the space
velocity achieving 10,000 h−1 . However, the effluent methanol
concentration diminishes continuously with the space velocity.
3.3. Effect of slurry recirculation flow rate
The difference in impinging stream reactor used in methanol
synthesis compared to other three phase reactor is that the cat-
alyst slurry is circulated by a pump from slurry part to reaction
part, and the catalyst slurry is atomized to fine drop when it goes
Fig. 7. Effect of space velocity on effluent methanol concentration.
Fig. 8. Effect of slurry recirculation flow rate on methanol productivity.
Fig. 9. Effect of slurry recirculation flow rate on effluent methanol concentration.
through the nozzles. Thus, the study of slurry recirculation flow
rate has great significance in this experiment.
As illustrated in Figs. 8 and 9, the methanol productivity
and effluent methanol concentration are shown as a function of
slurry recirculation flow rate, respectively. All these referenced
studies were conducted at 3.8 MPa, 230 ◦ C, space velocity of
10,000 h−1 , H2 /CO/CO2 ratio of 70/25/5 and the catalyst con-
centration of 10% by mass. Two opposed nozzles are used in the
experiment.
As expected, an increase in slurry recirculation flow rate is
advantageous to the reaction; the methanol productivity and
effluent methanol concentration are both increased. This can
be explained that the increase in slurry recirculation flow rate is
benefit to the inter-phase mass transfer because the inter-phase
disturbance is enhanced.
3.4. Effect of number of nozzles
The pressure flow nozzle is used in the experiment in order
to atomize the catalyst slurry, so the number of nozzle used in
the experiment has more or less effect on the methanol syn-
Fig. 10. Effect of number of nozzle on methanol productivity.
 L. Hu et al. / Chemical Engineering and Processing 46 (2007) 905–909
Fig. 11. Effect of number of nozzle on effluent methanol concentrations.
thesis reaction. Three series of experiments are conducted at
3.8 MPa, 230 ◦ C, space velocity of 10,000 h−1 , H2 /CO/CO2
ratio of 70/25/5, recirculation flow rate of 120 L h−1 and the
catalyst concentration of 10% by mass. Single nozzle, two
opposed nozzles and four opposed nozzles are used in the
experiment.
Methanol productivity and effluent methanol concentration
as a function of number of nozzles are shown in Figs. 10 and 11,
respectively. The results indicate that two opposed nozzles and
four opposed nozzles used in the experiment are better than
using single nozzle at nominally identical operating conditions.
This is because the catalyst slurry after atomized impacts each
other when the opposed nozzles are used, this promotes the inter-
phase interfusion and distribution so that the liquid mass transfer
increases.
4. Conclusions
A laboratory scale mini-pilot plant is successfully designed
and built to carry out research in the liquid-phase methanol
synthesis process in an impinging stream reactor.
Sustained operating conditions of temperatures approxi-
mately at 230 ◦ C, space velocity at 10,000 h−1 , high slurry
recirculation flow rate and two or four opposed nozzles rep-
resent a major extension of the operating range for this type
of reactor. A higher slurry recirculation flow rate is beneficial
to the inter-phase mass transfer because the inter-phase distur-
bance is enhanced, and the catalyst slurry after atomized impacts
each other when the opposed nozzles are used, this promotes the
inter-phase interfusion and distribution so that the liquid mass
transfer increases.
The data obtained, from this study, will help the scale-up
and commercialization of the methanol synthesis process in
impinging stream reactor significantly in later days.
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