Heat Transfer—Asian Research, 29 (4), 2000

Study on Solidification of Carbon Dioxide Using Cold Energy of

Liquefied Natural Gas

Yoshiyuki Takeuchi
Mitsubishi Heavy Ind. Ltd., Technical Headquarters, Hiroshima
Research & Development Center, Japan
Shogo Hironaka
Mitsubishi Heavy Ind. Ltd., Nagasaki Shipyard & Machinery Works, Japan
Yutaka Shimada
Chugoku Electric Power Co., Inc., Thermal Power Department, Japan
Kenji Tokumasa
Chugoku Electric Power Co., Inc., Technical Research Center, Japan

The present paper deals with solidification characteristics of carbon dioxide

around the gas feed nozzle of the flue gas from a thermal energy power plant. The
present experiment was carried out under dioxide contents between 3 and 50 vol%.
The results obtained indicate that the solidification fraction of carbon dioxide in-
creased with a decrease in cooling temperature. The solidification fraction of carbon
dioxide was expressed as a function of the nondimensional temperature and concen-
tration of the carbon dioxide. © 2000 Scripta Technica, Heat Trans Asian Res, 29(4):
249–268, 2000

Key words: Cold thermal energy, solidification, freezing, LNG, dry ice, heat
transfer

1. Introduction

The authors are working on development of the technology to utilize the cold enemy from
liquefied natural gas (LNG) at approximately –160 °C, which has so far been unused in power plants.
The “LNG combined cycle” process involves directly mixing the coolant gas with the flue (process)
gas to cool the gaseous CO2 present in the flue gas, thus forming dry ice which can be used to recover
the cold energy of the LNG gas.

The development of this process involves the following topics of research:

1. Understanding the solidification characteristics of the condensible gases (CO2, H2O) at low
temperatures and low concentration

a. Conditions for solidification of CO2/H2O gas mixtures: for example, influences of gas
composition, cooling temperature, gas flow velocity
© 2000 Scripta Technica
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 b. Understanding the physical properties of the solidified material: for example, particle
diameter, characteristics of condensation to cold surfaces

2. Understanding the heat transfer characteristics of the solidified material at low temperatures

The previous study [1] makes clear by experimentation how solidification temperature and
the presence of H2O influence the solidification ratio of CO2 gas when the flue (process) gas and
low-temperature cooling gas are mixed directly. The experiments conducted for that study used a
mixture of CO2, H2O, and N2 gases to simulate the flue (process) gas.

Stated simply, when the partial pressure of CO2 gas is 1 × 105 Pa, it solidifies at –78.5 °C, and
the temperature at which it solidifies gets lower as the partial pressure of the CO2 gas is decreased
(i.e., the concentration of CO2 gas is reduced). (See Fig. 1.)

The concentration of CO2 gas in the flue gas of the LNG combined cycle, which is the subject
of this research, is very low (approx. 3 mol%). With flue gas in this state, CO2 gas theoretically
solidifies at temperatures of –114 °C or lower. Based on their experimental results, however, the
authors discovered that the temperature at the inlet of a dry ice crystallizer (hereafter simply
“crystallizer”) must be –135 °C or colder in order to achieve a 90% solidification ratio. Possible
reasons for this phenomenon may include the following:

1. The shape of the flue gas feeder nozzle of the crystallizer may affect the mixing charac-
teristics of the low-temperature coolant gas and the mixing of the gases is not sufficient. Therefore,
not all CO2 gas is sufficiently cooled, so some of the CO2 gas passes through the crystallizer without
being solidified, thus lowering the solidification ratio.

Fig. 1. Correlation of CO2 concentration to solidification temperature.

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 2. The actual solidification temperature may differ from the theoretical solidification tempera-
ture due to the heat of solidification of the CO2 and H2O gas mixture in the process gas.

Another possible factor influencing the solidification ratio is the holding time in the crystal-
lizer, which in turn relates to the solidification speed.

With regard to these points, the authors investigated by experimentation the shape of the
process gas feed nozzle and its influence on gas flow. Based on those results the authors conducted
experiments using a single nozzle to determine how the concentration of the CO2 gas influences the
solidification ratio. This present paper contains the experimental results.

Nomenclature

D: inside diameter of outside pipe of nozzle mm

d1: inside diameter of coolant gas inlet section mm
d2: inside diameter of process gas inlet section mm
d3: width of solid particles µm
d4: length of solid particles µm
f: accumulated mass distribution mass %
mi: mass ratio
Mi: molecular weight
ρ: gas density kg/m3
µ: gas viscosity Pa⋅s
P: pressure Pa
R: gas constant J/K
Re: Reynolds number
S: CO2 gas solidification ratio %
S1: CO2 gas solidification ratio, when ratio is ≤ 90% %
S2: CO2 gas solidification ratio, when ratio is ≥ 90% %
T: temperature °C
Ti1: process gas inlet temperature °C
Ti2: coolant gas inlet temperature °C
Tr: critical temperature for solidification of CO2 gas when total pressure is 1 × 105 Pa °C
T0: nondimensional temperature (T − Tr) / T
u1: process gas inlet space velocity m/s
u2: coolant gas inlet space velocity m/s
θ: angle of conical section of outside pipe of gas feed nozzle deg

2. Gas Flow Analysis

2.1 Basic formulas related to gas flow

Around the outlet of the gas feed nozzles of the crystallizer, the process gas (including CO2
and H2O gas) is mixed with the coolant gas (mainly composed of N2 and O2). The cooled CO2 gas
and the steam in the process gas solidify. The shape of the wall of the crystallizer is thought to influence
these phenomena. However, it is difficult to establish by experimental means where exactly this

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solidification takes place. Therefore, in order to determine the state of gas flow and dispersion inside
the system, and to experimentally determine a suitable nozzle shape, an analysis was performed with
the assumption that the gas flow around the outlet of the nozzles was stable.

In the simulation, in order to analyze the flow of the mixed gas inside the crystallizer around
the outlet of the nozzle as well as the dispersion of the CO2 gas and water vapor, a finite element
method was performed using the following conservation differential equations:

1 ∂ ∂ ~ (1)
(√  ) + (ρu
gρ j) = sm
√g ∂t ∂xj

1 ∂ ∂ ~ ∂p (2)
(√
g ρui) + (ρujui − τij) = − + si
√g ∂t ∂xj ∂xi

where

xi: absolute coordinates (i = 1, 2)

ui: absolute velocity component of the fluid in the xi direction
~
uj: relative speed (ui − ucj) of the fluid relative coordinate system of the local area moving
with velocity ucj
p: piezo pressure = ps − ρ0gmxm.
In this formula, ps is static pressure, ρ0 is the reference density, and gm is the gravitation
acceleration.
τij: stress tensor component
sm: mass source
si: momentum source
g :
√ metric tensor determinant

The fluid is an ideal mixed gas made up of N2, CO2, and H2O. Its density is a function of the
relative mass of the various components as well as temperature as given by the following formula:

P (3)
ρ=
mi
RT ∑
i Mi

The Re number around the outlet of the gas feed nozzles is 4.1 × 105. Since this is greater than
the critical Re number, thus causing turbulent flow, the high-Re-number-formula k–ε model was used.
Considering the axial symmetry of the gas inlet nozzle, the model used for the analysis was a stable
two-dimensional axially symmetric model. A numerical analysis was performed using the implicit
method with the above-mentioned stable two-dimensional formulas.

2.2 Conditions for calculation

As shown in Fig. 2, in the cylindrical crystallizer of a commercial plant, there are multiple gas
feed nozzles. It is believed that most of the CO2 gas around the outlets of these gas feed nozzles is

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 Fig. 2. Configuration of dry ice crystallizer.

solidified. With this in mind, the authors conducted this experiment with a single nozzle of the same
specifications as the gas feed nozzles which would be found in a commercial plant, namely:

a. The main body/outlet portion of the nozzle is cylindrical in shape; the base of the nozzle is
conical.

b. Coolant gas is blown upward from the bottom portion of the apparatus.

c. Process gas is blown into the center of the conical section via a cylindrical nozzle. Then the
direction of the flow of the gas is reversed when it hits the cap installed on the end of the cylindrical
nozzle, and then finally the gas flows into the area with the coolant gas.

d. The wall of the upper section of the nozzle is thermally insulated and the temperature
distribution is made uniform.

Boundary conditions are as follows:

a. The angle of the wall of the conical section of the outside pipe is θ = 30° or θ = 45° (two
different types).

b. The inlet temperature for process gas into the nozzle section is –5 °C.

c. The inlet temperature for coolant gas into the nozzle section is –150 °C.

d. Inlet space velocity of process gas:

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 Based on the results of the basic testing (see the previous study [1]), in order to prevent the
formation of solids on the pipe walls, and to carry the solids out of the crystallizer in the flowing air,
the condition for the inlet pipe (including the flow velocity) of the process gas is u1 = 10 m/s.

e. Coolant gas inlet space velocity: u2 = 10 m/s.

f. The Reynolds number of the process gas at the cap section, before being blown out, is:

Re = d2 × u1 × ρ / µ = 5.0 × 107 (4)

g. Gas composition:

An analysis was performed for gas composition for the following two cases:

1Standard process gas (vol%)

CO2 = 3.4, H2O = 0.8, N2 = 80.9, O2 = 14.9

2High-concentration CO2 gas (vol%)

CO2 = 64.0, H2O = 1.7, N2 = 34.3, O2 = 0.0

h. In the results of the previous study [1], it was found that the solidification ratio of CO2 at
–140 °C was 100%.

i. Analysis was performed using a stable two-dimensional axially symmetric model. The
model shown in Fig. 3 was divided into a mesh with 50 divisions horizontally, and 70 divisions
vertically.

j. Dimensions: D = 84, d1 = 33, d2 = 11 (mm).

2.3 Results of analysis

2.3.1 Gas flow velocity distribution

Considering the symmetry of the gas flow, the flow velocity distribution was calculated for
the section on the left side of the gas feed nozzle only. This velocity distribution is shown in Fig. 4.

Coolant gas flows up along the walls from the bottom of the conical section. The process gas,
which includes CO2 gas, flows in through the inside pipe (the center of the inside pipe is shown on
the right portion of the figure). The direction of the flow of the process gas is reversed by the cap at
the end of the cylindrical nozzle and the gas is blown down into the coolant gas flow, but its direction
is quickly reversed by the flow of the coolant gas and is carried up along the inside wall of the outside
pipe.

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Fig. 3. Flow analysis model of gas feed nozzle in crystallizer (dimensions in mm).

Fig. 4. Gas velocity magnitude.

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 At this time, the flow velocity of the process gas is reduced to between 3 and 4 m/s, but the
Re number for the gas immediately after it is blown off the cap is a very turbulent Re = 1.5 to 2.0 ×
106, so it mixes very thoroughly with the coolant gas and it attains a flow velocity of 3.7 to 7.5 m/s.

2.3.2 Gas temperature distribution

The following shows some representative results of numerical simulations.

1. Cone wall angle θ = 30°; standard process gas:

Figure 5 shows the temperature distribution for θ = 30°. Before the process gas reaches the
wall of the outside pipe it reaches the target temperature of –140 °C or below in the conical section.
The CO2 gas solidifies to become dry ice in the cold (≤ –140 °C) region.

Comparing these results with Fig. 4, we can see that a high flow velocity is maintained in the
cold (≤ –140 °C) region, and it can be supposed that solids are prevented from forming on the wall.

2. Cone wall angle θ = 45°; standard process gas:

Figure 6 shows the temperature distribution for θ = 45°. The temperature distribution is more
spread out due to the increased angle θ. However, as in Fig. 5, the target temperature of –140 °C or
below is reached in the conical section.

3. High-concentration CO2 gas:

Figure 7 shows the results of the numerical analysis assuming a high concentration of CO2
gas (CO2 = 64.0, H2O = 1.7, N2 = 34.3, O2 = 0.0 vol%) with a cone wall angle of θ = 30°.

Fig. 5. Temperature distribution (θ = 30°, CO2 = 3%).

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 Fig. 6. Temperature distribution (θ = 45°, CO2 = 3%).

In this case, because the concentration of CO2 gas is relatively high, the heat required for
solidification is greater, and the solidification region (temperature ≤ –140 °C) is shifted up in
comparison with examples 1 and 2, but otherwise no significant difference can be observed.

2.3.3 Selection of shape of gas feed nozzle

For application in a commercial plant, in order to keep the equipment as compact as possible,
it is necessary to uniformly diffuse a large volume of process gas (e.g., 1.36 × 106 Nm3/h for a
118-MW-class power plant) and feed it into a large dry-ice crystallizer and then uniformly mix it with
the coolant gas in a short period of time. However, with a commonly used free-flow nozzle, for

Fig. 7. Temperature distribution (θ = 30°, CO2 = 64%).

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example, a high flow velocity of 30 m/s or greater was required and this would result in great pressure
loss, so the above-mentioned new type of nozzle was examined. It was judged on the basis of gas
distribution calculated by the gas flow analysis that the new type of nozzle enabled highly efficient
solidification of CO2 gas around the outlet of the gas feed nozzle. Therefore, in order to confirm the
simulation results, actual experimentation was carried out with nozzles having the following specifi-
cations to evaluate their performance:

1. Conical lower section

2. Angle θ of bottom section of outside pipe:

Almost no difference in performance was observed between θ = 30° and θ = 45°, but
considering the goal of achieving compact equipment, the outside pipe with θ = 30° design was
adopted.

3. The shape of the process gas feed nozzle was the same as that used for the numerical
simulation.

3. Test Apparatus and Experimental Procedure

Based on the results of the above-mentioned gas flow analysis, in order to predict the properties
of the CO2 gas solidification process in a commercial plant, a single nozzle with the same specifica-
tions as those to be used in a commercial plant was obtained and experimentation conducted with this
single nozzle. In the following description of the experiment, this single nozzle proper is simply called
the “dry ice crystallizer.”

The details of the test apparatus and experimental procedure are as described below. Figure 8
shows a sketch of the test apparatus. The procedure uses simulated process gas which simulates flue
gas containing CO2 gas and which is produced by mixing nitrogen gas and CO2 gas, achieving a

Fig. 8. Schematic diagram of test apparatus.

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constant concentration. The flow rate is measured with thermal flow meters shown by 5, 6, and 7in
Fig. 8. The measurements are accurate within ± 0.1 liter/h. The simulated process gas is cooled by
being bubbled through the water in the humidifier shown by 9 in Fig. 8 which is kept at a fixed
temperature, and the water in the cooled gas is removed by a trap. The process gas which is
steam-saturated is fed into the dry ice crystallizer shown by àin Fig. 8. The concentration of water
vapor in this wet process gas was measured in a prior separate experiment, in which the mixed gas
was cooled by being circulated through a trap cooled by liquid nitrogen, and the mass of the water
condensation in the trap was measured precisely (the measurement is accurate within ±0.1%).

On the other hand, coolant gas is created by evaporating liquid nitrogen in an evaporator and
the temperature adjusted in the precooler indicated by 8 in Fig. 8. After that, the coolant gas is
precooled by being passed through the coil indicated by èinside the thermostat indicated by âwhich
is installed on the dry ice crystallizer. Then it is fed to the dry ice crystallizer. The coil is a copper
pipe, 10 m in length with an internal diameter of 20 mm, formed in a coil shape with a diameter of
200 mm. The purpose of the coil is to adjust the temperature of the coolant gas to be the same as that
of the inside wall of the dry ice crystallizer by circulating the coolant gas through the coil, thus
rendering it the same temperature as that of the thermostat.

The process gas and coolant gas are each fed into the inlet of the crystallizer. The gases then
become mixed in the conical section of the dry ice crystallizer before flowing into the dry ice
crystallizer proper. The pipe connected to the process gas inlet nozzle has a pipe-inside-a-pipe
structure. In order to prevent the coolant gas from cooling the pipe containing the process gas, causing
the moisture in the process gas to condense on the inner surface of the pipe, heated dry air is circulated
through the outer pipe, and the process gas kept at 0 °C. The flow rate of the process gas is
approximately 1/8 the flow rate of the coolant gas when calculated on a molar ratio. The process gas
is cooled by the cold energy of the coolant gas. Then when the CO2 in the mixed gas reaches the
temperature of solidification of CO2, microparticles of dry ice are formed. These microparticles are
then carried by the mixed gas to the cyclone indicated by á where they are separated from the gas.
The microparticles then accumulate in the bottom of the cyclone.

The dry ice crystallizer and cyclone apparatus shown in Fig. 9 is set inside the thermostat in
order to prevent heat radiation and maintain a fixed cooling temperature. The temperature inside the
thermostat is set to be constant between –70 and 160 °C by spraying liquid nitrogen from nozzles
inside the thermostat. In order to prevent uneven temperature distribution within the thermostat, two
fans, indicated by ãand äin Fig. 8, are controlled by a temperature regulator. (The temperature control
is accurate within ± 0.1 °C.)

Three T-type 0.1-mm-diameter wire thermocouples are located inside the dry ice crystallizer
to measure the temperature distribution which is recorded by a 24-point chopper bar-type high-speed
recorder indicated by çin Fig. 8.

Each thermocouple was calibrated with a standard scale precise to 0.05 °C. It is estimated that
the temperature readings are accurate to within ±0.1 °C.

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 Fig. 9. Detail of dry ice crystallizer.

The solidification ratio of the CO2 gas was calculated using a gas chromatograph to analyze
and compare the composition of the gas at the inlet and outlet of the dry ice crystallizer. The gas
chromatograph can measure the concentration of CO2 gas with an accuracy of 10 ppm.

The specifications of the main equipment are as follows.

1. Dry ice crystallizer (àin Fig. 8, see also Fig. 9):

Material: Pyrex glass

Dimensions: 84 inside diameter × 600 length × 9 wall thickness (mm)

Angle of bottom portion of outside pipe: 30°

Thermometer: T-type thermocouples (3 units) (using 0.1-mm-diameter wire)

Placed vertically inside the thermostat

2. Thermostat (âin Fig. 8):

Dimensions: 750 W × 1000 L × 1950 H (mm)

Lowest maintainable temperature: –180 °C

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 Thermometer: T-type thermocouple (using 0.1-mm-diameter wire)

Other: 200 × 200-mm view port (2)

Thermometer: T-type thermocouple (6 units) (using 0.1-mm-diameter wire)

3. Liquid nitrogen evaporator:

Quantity of produced gas: 10 Nm3/h

4. Precooler (8in Fig. 8):

Dimensions: 750 W × 1400 L × 750 H (mm)

Type of gas: N2

Coolant gas capacity: up to 6 Nm3/h

Gas temp.: –100 °C to –160 °C at inlet of crystallizer

5. Humidifier (9in Fig. 8):

Dimensions: 750 W × 1400 L × 750 H (mm)

Humidifying temp.: 25 °C to 80 °C

Internal pipe for humidifier: 150 inside diameter × 150 height (mm)

Thermostat: 230 inside diameter × 250 height (mm)

Thermometer: T-type thermocouples (using 0.1-mm-diameter wire)

4. Experimental Results and Further Considerations

4.1 Factors influencing the solidification ratio of CO2

The following is a list of factors which are thought to influence the solidification ratio of CO2
gas.

1. Shape of both the crystallizer and the nozzle:

These influence the properties of gas flow and mixing characteristics of the gas.

2. Operating conditions:

Gas flow speed, cooling temperature may affect the CO2 gas solidification ratio.

3. Concentration of CO2 gas:

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 Supersaturation ratio (vapor pressure/equilibrium vapor pressure) has an effect on the forma-
tion speed of even clusters [3–5].

4. Inclusion of impurities:

It is easy for uneven clusters to form if the process gas includes H2O.

We can accurately design a commercial plant based on the information of the above factors,
including the results of this numerical simulation and the law of similarity. An overview of item 4
was given in the previous report [2]. In item 2, the Re number of the gas flow speed for the commercial
plant can be evaluated by the numerical simulation. In this paper, we will report on the influence of
temperature in item 2, and information in item 3 that was gained by examining the experimental
results.

4.2 Effect of temperature on solidification ratio

For the process gas, the correlation between cooling temperature and solidification ratio was
made clear by experimentation. Figure 10 shows a plot of the experimental data. The curves shown
in the figure are drawn by joining individual measured data points. The results of this experiment
show the following:

1. When CO2 gas is present in the process gas at a low concentration, it can be solidified by
lowering the cooling temperature. The relationship between cooling temperature and solidification
ratio is clearly shown in Fig. 10.

2. When the CO2 gas concentration is low, as in the LNG combined cycle process gas (3
mol%), the supersaturation ratio (113/78.5 = 1.4) also becomes low. As a result, homogeneous
nucleation occurs slowly, and it becomes easy to reach an overcooled state [6]. It is believed that in

Fig. 10. Solidification ratio of CO2 as a function of temperature.

262
such a case, in order to reach S > 90%, it would be necessary to lower the temperature to lower than
the theoretical cooling temperature of –135 °C.

3. The higher the concentration of the CO2 gas, the closer the starting solidification tempera-
ture approaches –114 °C.

4.3 Nondimensional temperature formula for solidification ratio

The factors which affect the solidification ratio (S) of the CO2 gas include:

Tr: The temperature of solidification when total pressure of CO2 gas is 1 × 105 Pa

T: Cooling temperature

C: Concentration of CO2 gas

The definition of nondimensional temperature is

T0 = (T − Tr) / T (5)

On the other hand, the relationship between the solidification ratio of CO2 gas and cooling tempera-
ture, as shown in Fig. 10, can be described as follows:

1. When the solidification ratio of CO2 gas is lower than 90%, the relationship between
temperature and solidification ratio can be seen to be almost linear, so the effect of the cooling
temperature on the solidification ratio is large.

2. When the solidification ratio of CO2 gas is higher than 90%, the influence of temperature
on solidification ratio is much smaller.

Therefore, two formulas were obtained from the experiment (depending on whether the solidification
ratio was above or below 90%). The formulas are as follows:

For S ≤ 90%

S1 = 1480 × T0 + 0.0147C2 + 0.728 × C + 734 (6)

For S > 90%

S2 = −94.0 × T0 + 0.00170 × C2 + 0.0127 × C + 131 (7)

where

S1, S2 are the solidification ratio of the CO2 gas (%)

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 Fig. 11. Solidification ratio of CO2 as a function of nondimensional temperature.

C is the concentration of CO2 gas (mol%)

Figure 11 shows a comparison between the experimentally determined formulas (6) and (7),
and the experimentally measured values. For the temperature range for which the solidification ratio
is less than approximately 90%, the solidification ratio S1 increases greatly as the nondimensional
temperature T0 decreases. When the solidification ratio is greater than approximately 90%, the
solidification ratio S2 increases only slightly as T0 decreases. Within each region, the solidification
ratio S has a nearly linear relationship with T0. The individually measured data match the experimen-
tally determined formulas very closely. For the actual data measured in this experiment, the largest
deviations from the experimentally determined formulas were:

• Deviation of ±1% for S1 ≤ 90%

• Deviation of ±2% for S2 > 90%

By using the nondimensional experimentally determined formulas shown above, given the
CO2 gas concentration (C) and the cooling temperature T, the values of S1 and S2 can be calculated.

4.4 Effect of concentration of CO2 gas on solidification ratio

Figure 12 shows the solidification ratio of CO2 as a function of concentration of CO2 gas.

It was confirmed that for any given temperature, the higher the concentration of CO2 gas, the
higher the solidification ratio becomes.

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 Fig. 12. Solidification ratio of CO2 as a function of concentration of CO2 gas.

It was also confirmed that because the flue gas produced by the LNG combined cycle contains
a relatively low (3 mol%) concentration of CO2 gas, the gas must be cooled to about –140 °C in order
to achieve a CO2 solidification ratio of 90% or greater.

4.5 State of formation of solids in the crystallizer

Figure 13 is a photograph taken through the view port of the thermostat showing the state of
the solids formed from the CO2 gas. It was confirmed that the white solid clusters (dry ice mixed with
ice) as shown in Fig. 13 are first formed in the lower portion of the crystallizer, near the inlet nozzle.
Figure 14 is one frame from a video film taken with a 200× power video microscope showing an
image of solids formed from the CO2 gas. This image was used to measure the diameter of 215 solid
particles to determine the cumulative diameter distribution, which was plotted on a Rosin–Rammler
diagram in Fig. 15, where d3 is the width and d4 is the length. From these results, it can be seen that
the diameters of the solid particles are extremely evenly distributed, with approximately 50% of the
particles having a diameter very close to the median diameter (d50) of d = 150.

In addition, it was observed that the formed solids are relatively dry in nature, and therefore
do not stick to the crystallizer walls, but rather are carried out of the crystallizer rather easily in the
gas flowing at about 1 m/s.

As shown above, according to the results of the flow analysis, after the process gas is blown
out of the cap section, the temperature of the process gas is lowered to the solidification temperature
of CO2 gas, thereby causing solids to form after passing through the cap section. Then the formed
solids are carried away in gas flowing at 1 m/s or greater. Therefore, with this shape nozzle it is
believed that the solid particles have no significant effect on the gas flow pattern around the gas inlet
nozzle.

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 Fig. 13. Products of CO2 solidification.

Fig. 14. Solid of CO2 and H2O at –140 °C.

266
 Fig. 15. Diameter distribution of solid particles (Rosin–Rammler diagram).

5. Conclusions

Up until now, when ultracold LNG is converted back to gas to be used as fuel, its cold energy
has simply been released, unused. With the goals of developing a system to make effective use of this
cold energy and reducing emissions of CO2 gas which is a factor in global warming, the authors
continue to develop a system to solidify and collect CO2 gas present in the flue gas of power plants
which use LNG. There are various factors which have an influence on the solidification ratio, such
as the solidification speed which is in turn influenced by the residence time in the crystallizer, and so
on.

With this background, this report summarizes the results of the authors’ gas flow analysis of
the area around the outlet of a single gas feed nozzle in a dry ice crystallizer which has many gas feed
nozzles. Based on the results of this analysis, an experimental apparatus was fabricated, consisting of
a single nozzle with specifications almost identical to those of the many nozzles used in a commercial
plant. The experiment clarified the effects of the composition of CO2 gas on the solidification ratio
of the CO2 gas inside the nozzles. The results can be summarized as follows:

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 1. The relationship between the solidification ratio of the CO2 gas and the cooling temperature
was quantitatively established.

2. The concentration of CO2 gas in the mixed gas influences the solidification ratio of the CO2
gas, but in order to achieve a 90% solidification ratio, it is sufficient that the temperature at the gas
feed nozzle is less than about –140 °C.

3. Based on experimental data, formulas for the relationship between the solidification ratio
at the outlet of the gas feed nozzle and the cooling temperature were proposed. For a plant with the
specifications used in this experiment, these formulas can be used to accurately calculate the
solidification ratio based on the concentration of CO2 gas (C) and cooling temperature (T).

The solid particles produced in this experiment are extremely fine, with an average particle
diameter of 150 µm. For a commercial plant it is necessary to store the separated and collected solids
in a container and transport it to a storage facility. The density of the solid product will have a
significant effect on transportation costs. In order to improve this aspect of the process, the authors
are planning to modify the process which increases the particle size and compresses the produced
particles into a solid shape, thus increasing the apparent density.

Future topics of research include:

• Understanding the factors influencing the formation rate of solids

• Understanding the properties of the solid crystals and the influence of H2O

• Study on procedures to prevent the formed solids from sticking to the walls of the
equipment.

Literature Cited

1. Takeuchi Y. Trans JSME 1997;63B:654–659. (in Japanese)

2. Komiya H. Handbook of greenhouse problem of Earth. IPC; 1990. p 71.
3. Arakawa. Fundamental technology on powder. Nikkankougyou; 1992.
4. Nishinaga. Fundamental technology on crystal growth. Baifuukan; 1997.
5. Jpn. Soc. Crystal Growth. Handbook of crystal growth. Kyouritsu Shyuppann; 1995. p 141.
6. Inaba H. Phenomena of heat transfer and application under low temperature conditions.
Youkendou; 1996. p 97.

"F F F"

Originally published in Trans JSME (B), 64, 1998, 2640–2647.

Translated by Yoshiyuki Takeuchi, Mitsubishi Heavy Ind. Ltd., Technical Headquarters, Hiroshima
Research & Development Center, 6-22, 4-Chome, Kan-on-shin-machi, Nishi-ku, Hiroshima,
Japan 733-8553.

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