U.S. patent application number 12/063819 was filed with the patent office on 2009-02-05 for method for production, substitution, or mining of gas hydrate.
Invention is credited to Yojiro Ikegawa, Michal Svoboda, Xenia Svobodova.
Application Number | 20090032248 12/063819 |
Document ID | / |
Family ID | 37771681 |
Filed Date | 2009-02-05 |
United States Patent
Application |
20090032248 |
Kind Code |
A1 |
Svoboda; Michal ; et
al. |
February 5, 2009 |
METHOD FOR PRODUCTION, SUBSTITUTION, OR MINING OF GAS HYDRATE
Abstract
A gas hydrate is produced by injecting guest molecules into
voids in a layer of which temperature and pressure condition allows
the guest molecules to cause to form hydrate, in a form of emulsion
where liquid of the guest molecules is dispersed in water as minute
particles having a size of less than a size of voids, and thereby
dispersing the guest molecules uniformly into the voids in the
layer.
Inventors: |
Svoboda; Michal; (Praha,
CZ) ; Svobodova; Xenia; (Praha, CZ) ; Ikegawa;
Yojiro; (US) |
Correspondence
Address: |
NOTARO & MICHALOS P.C.
100 DUTCH HILL ROAD, SUITE 110
ORANGEBURG
NY
10962-2100
US
|
Family ID: |
37771681 |
Appl. No.: |
12/063819 |
Filed: |
August 25, 2006 |
PCT Filed: |
August 25, 2006 |
PCT NO: |
PCT/JP2006/316726 |
371 Date: |
February 14, 2008 |
Current U.S.
Class: |
166/249 ;
166/279 |
Current CPC
Class: |
E21B 43/164 20130101;
Y02C 20/40 20200801; Y02P 90/70 20151101; C10L 3/06 20130101; Y02C
10/14 20130101; E21B 41/0099 20200501; C07B 63/02 20130101; C10L
3/108 20130101; E21B 41/0064 20130101 |
Class at
Publication: |
166/249 ;
166/279 |
International
Class: |
E21B 43/00 20060101
E21B043/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 26, 2005 |
JP |
2005-245769 |
Claims
1. A method for production of gas hydrate, which is characterized
in that guest molecules are injected into voids in the layer of
which temperature and pressure condition allows the guest molecules
to cause to form hydrate, in a form of emulsion where liquid of the
guest molecules is dispersed in water as minute particles having a
size of less than a size of the voids.
2. The method for production of gas hydrate according to claim 1,
wherein the heating value per unit volume of the emulsion is
controlled by varying the ratio of the liquid of the guest
molecules and the water in the emulsion.
3. The method for production of gas hydrate according to claim 1,
wherein the production rate of the hydrate is controlled by varying
the size of the liquid minute particles of the guest molecules in
the emulsion.
4. The method for production of gas hydrate according to claim 1,
wherein an interfaces between the minute particles of the guest
molecules and the water were activated by irradiating the emulsion
with ultrasonic waves.
5. The method for production of gas hydrate according to claim 1,
wherein, by irradiating the emulsion with ultrasonic waves
continuously, the production of the hydrate during irradiation is
repressed.
6. The method for production of gas hydrate according to claim 1,
wherein the guest molecules are CO.sub.2.
7. A method for substitution of gas hydrate, which is characterized
in that, to voids in a layer where hydrate of first guest molecules
exists, an emulsion in which a liquid of second guest molecules is
dispersed in water as minute particles having a size of less than
the size of the voids is injected, wherein the second guest
molecules can form hydrate under a higher temperature and lower
pressure condition as compared with the temperature and pressure
condition under which the first guest molecules forms the hydrate;
and thereby the hydrate of the first guest molecules is decomposed
by heat which is generated when the hydrate of the second guest
molecules is produced.
8. The method for substitution of gas hydrate according to claim 7,
wherein the heating value per unit volume of the emulsion is
controlled by varying the ratio of the liquid of the second guest
molecules and the water in the emulsion.
9. The method for substitution of gas hydrate according to claim 7,
wherein the production rate of the hydrate of the second guest
molecules is controlled by varying the size of the liquid minute
particles of the second guest molecules in the emulsion.
10. The method for substitution of gas hydrate according to claim
7, wherein an interfaces between the minute particles of the second
guest molecules and the water were activated by irradiating the
emulsion with ultrasonic waves at the early stage of the
substitution.
11. The method for substitution of gas hydrate according to claim
7, wherein, by irradiating the emulsion with ultrasonic waves
continuously, the production of the hydrate of the second guest
molecules during irradiation is repressed.
12. The method for substitution of gas hydrate according to claim
7, wherein the progress for decomposition of the hydrate of the
first guest molecules and the progress for production of the
hydrate of the second guest molecules are estimated by at least one
or more of the change in temperature of the layer, the change in
passing speed of ultrasonic waves through the layer, and the change
in permeability of the emulsion into the voids.
13. The method for substitution of gas hydrate according to claim
7, wherein the first guest molecules are CH.sub.4, and the second
guest molecules are CO.sub.2.
14. A method for mining of gas hydrate, which is characterized in
that, to voids in CH.sub.4 hydrate layer, an emulsion in which a
liquid CO.sub.2 is dispersed in water as minute particles having a
size of less than the size of the voids is injected, wherein the
emulsion is used as a heating agent for decomposing the CH.sub.4
hydrate existing in the voids.
15. A method for mining of gas hydrate, which is characterized in
that, to voids in a layer which is rested on a CH.sub.4 hydrate
layer and is under the temperature and pressure condition that
CO.sub.2 can forms hydrate, an emulsion in which a liquid CO.sub.2
is dispersed in water as minute particles having a size of less
than a size of the voids is injected in order to form a seal layer
of CO.sub.2 hydrate; and then the emulsion is injected to voids in
the CH.sub.4 hydrate layer so that CO.sub.2 hydrate is produced
while decomposing the CH.sub.4 hydrate existed in the voids by heat
of reaction in the CO.sub.2 hydrate production, thus the CH.sub.4
hydrate is replaced with the CO.sub.2 hydrate while recovering
CH.sub.4 gas.
16. A method for mining of gas hydrate, which is characterized in
that, to voids in a layer which is rested on a CH.sub.4 hydrate
layer and is under the temperature and pressure condition that
CO.sub.2 can forms hydrate, an emulsion in which a liquid CO.sub.2
is dispersed in water as minute particles having a size of less
than a size of the voids is injected in order to form a seal layer
of CO.sub.2 hydrate; the emulsion is injected to voids in a layer
which is rested under the CH.sub.4 hydrate layer in order to
produce CO.sub.2 hydrate and to cause the temperature of the layer
rested under the CH.sub.4 hydrate layer to rise by heat of reaction
in the CO.sub.2 hydrate production, by which risen temperature the
CH.sub.4 hydrate existing in the CH.sub.4 hydrate layer is
decomposed from the lower side of the CH.sub.4 hydrate layer; and
the CH.sub.4 gas is collected by the seal layer in order to recover
the CH.sub.4 gas to the ground, while the strength of the layer
after mining of the CH.sub.4 hydrate is restored by injecting the
emulsion into the layer so as to form CO.sub.2 hydrate therein.
Description
TECHNICAL FIELD
[0001] This invention relates to methods for production,
substitution, and mining of gas hydrate. More particularly, this
invention relates to a method for fixation of carbon dioxide
(CO.sub.2), and a method useful for mining of methane (CH.sub.4)
hydrate by substitution utilizing the fixation.
BACKGROUND OF ARTS
[0002] In order to prevent the global warming due to the release of
enormous amount of CO.sub.2, it has been studied to fixate CO.sub.2
to submarine layer, lake bottom layer, permafrost, or the like by
hydrating CO.sub.2. Meanwhile, vast amounts of CH.sub.4 hydrate lie
under submarine layer or the like have been attracted as a new
energy source, and thus the mining of CH.sub.4 hydrate has been
studied. Further, it has been also studied to mine CH.sub.4 while
fixating CO.sub.2 by substituting CH.sub.4 molecules in CH.sub.4
hydrate to CO.sub.2 molecules.
[0003] For instance, a research paper (Non-patent Literature 1)
discloses about the substitution of CH.sub.4 molecules in CH.sub.4
hydrate to CO.sub.2 molecules. In this research paper, it is
discussed thermodynamically that methane as guest molecules in
hydrate lattice is substituted to carbon dioxide without
decomposing the hydrate lattice under the mixture state of CH.sub.4
gas, carbon dioxide, water, CH.sub.4 hydrate and carbon dioxide
hydrate.
[0004] Further, a method for fixation of carbon dioxide has been
proposed, wherein carbon dioxide is introduced to the underground
CH.sub.4 hydrate layer in order to substitute methane with carbon
dioxide and fixate the carbon dioxide as carbon dioxide hydrate to
the hydrate layer, and extract natural gas to the Earth's surface
(Patent Literature 2). Since a condition where CH.sub.4 hydrate
exists stably also functions as a condition where carbon dioxide
hydrate exists stably, the carbon dioxide hydrate can be produced
by injecting gaseous or liquid carbon dioxide to the CH.sub.4
hydrate layer through a penetrating injection pipe, while by the
exothermal reaction at this production the CH.sub.4 hydrate can be
decomposed. Then, the methane gas is recovered to the ground
through a separate exhaust pipe.
[0005] Incidentally, as a method for mining of gas hydrate, it has
been proposed to emit a high speed jet flow to gas hydrate layer
through a mining pipe which was impacted to the layer having the
gas hydrate layer, in order to cut and break the gas hydrate and
recover it as a gas including mixture fluid to the ground, while
filling cavities in the layer which are created by the recovery of
gas hydrate with the composition of the high speed jet flow (Patent
Literature 1). As the composition of the high speed jet flow, a
minute grain material which includes slime, cement type hardener,
and/or industrial by-product such as blast furnace slag in slurry
which is prepared by kneading water and silt, cohesive soil or the
like is used.
Patent Literature 1: Japanese Patent Unexamined Publication
2003-214082 (JP 2003-214082 A)
Patent Literature 2: Japanese Patent Unexamined Publication HEI
6-71161 (JP HEI 6-71161 A)
[0006] Non-Patent Literature 1: Kazunari Ohgaki, Kiyomitsu Takano,
Masairi Moritoki, "Utilization of CH.sub.4 hydrate and reservation
of CO.sub.2 in Nankai trough", Collection of Chemical Engineering
Essay, Japan, 20 (1), 1994.01, pp. 121-123
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0007] The method for mining of the gas hydrate disclosed in the
Patent Literature 1, however, is useless for fixating CO.sub.2,
because in the method the gas hydrate is merely recovered by
cutting and breaking it in the layer. In addition, most of the
layer as targets for mining of gas hydrate are ocean sedimentary
layer where solid phases such as sand particles are connected to
each other by the presence of CH.sub.4 hydrate. Therefore, although
the cavities which have been created after the mining are filled
with the composition of the high speed jet flow, there is a fear of
causing caving or landslide of the layer around the region cut and
broken by the high speed jet flow, or causing cracks which is
followed by embrittlement or destruction of the layer around the
region cut and broken by the high speed jet flow before the
fluidity of the composition of the high speed jet flow settles and
the composition fixes. Thereby, CH.sub.4 hydrate may come to the
surface and is dissolved naturally, and then the situation that the
effluence of CH.sub.4 gas to the ground can not be controlled may
be happened. Further, the substitution of gas hydrate with the
minute grain material which includes slime, cement type hardener,
and/or industrial by-product such as blast furnace slag in slurry
which is prepared by kneading water and silt, cohesive soil or the
like may bring the fear of additional environmental pollution.
[0008] According to the method for fixation of carbon dioxide of
the Patent Literature 2, since liquid CO.sub.2 of almost 100%
concentration is injected without mixing with water, the area of
the interface between the liquid CO.sub.2 and water where the
hydrate producing reaction occurs is restricted and is very small,
and thus there is a problem that the reaction is slow. In addition,
although the ratio of water and CO.sub.2 is important for the
CO.sub.2 hydrate producing reaction, it is hardly possible to
maintain the ratio of water and CO.sub.2 uniformly in the void of
the layer when injecting the liquid CO.sub.2 of almost 100%
concentration into the layer. Therefore, it is very difficult to
fixate a large amount of CO.sub.2 as CO.sub.2 hydrate, and it is
also difficult to substitute it efficiently with a large amount of
methane. Thus, the method is impractical when the fixation of a
large amount of CO.sub.2 at once is demanded. Further, since the
ocean sedimentary layer where the CH.sub.4 hydrate exists is
unconsolidated one, when a large amount of liquid CO.sub.2 is
injected there, the liquid CO.sub.2 will come to rise by buoyancy
in the case that the reaction rate is slow. Because, the specific
gravity of liquid CO.sub.2 is lighter than that of seawater. Thus,
there is a fear that the leak of liquid CO.sub.2 to the ocean
bottom before the CO.sub.2 hydrate is produced. Furthermore, since
it is difficult to predict where and how the interface between the
liquid CO.sub.2 and water is moved to the void in layer, it becomes
difficult to predict the distribution of temperature rising of the
layer due to the heat generation on the production of CO.sub.2
hydrate, and to control the temperature of the layer so as to
create efficiently the decomposition of CH.sub.4 hydrate. Thus,
there is a problem that the control of production of gas hydrate
and the control of decomposition of gas hydrate are difficult.
[0009] In the case of low temperature and high pressure environment
where CO.sub.2 hydrate is produced, however, CO.sub.2 hydrate can
be produced at higher temperature and lower pressure side as
compared with CH.sub.4, and thus, it is the environment where
CO.sub.2 hydrate is retained stably as is the case with CH.sub.4
hydrate, and which can fixate CO.sub.2 hydrate. Therefore, in order
to put the technique for fixating CO.sub.2 by hydration and the
technique for mining of CH.sub.4 hydrate by substituting CH.sub.4
hydrate with CO.sub.2 hydrate to practical use, it is desired to
accelerate the production rate of CO.sub.2 hydrate.
[0010] This invention aims to provide to methods for production,
substitution, and mining of gas hydrate, which can accelerate
production rate of the gas hydrate.
Means for Solving the Problems
[0011] The method for production of gas hydrate according to the
present invention for attaining such an objective is characterized
in that guest molecules are injected into voids in the layer of
which temperature and pressure condition allows the guest molecules
to cause hydration, in a form of emulsion where liquid of the guest
molecules is dispersed as minute particles having a size of less
than the size of voids in water.
[0012] The ratio of the liquid minute particle of guest molecules
and water as dispersing medium, which constitute the emulsion, is
not particularly limited to a certain value. Although it is
preferable that the ratio is adjusted to a value suitable for
producing hydrate, it is possible in some cases that the ratio of
the liquid of guest molecules and water is varied in order to
control the heating value per unit volume of emulsion. Further, it
is also possible that the size of the liquid minute particles of
guest molecules in emulsion is varied in order to control the
production rate of hydrate. These controls are useful for
preventing the temperature rising of the layer associated with the
production of gas hydrate from reaching a temperature of not
producing the hydrate or a temperature at which the hydrate becomes
unstable.
[0013] In the present invention, the emulsion may be injected into
the layer, as it is, without giving a particular operation. It is
also possible, however, to irradiate emulsion with ultrasonic waves
in order to activate the interfaces of guest molecules, or to
irradiate emulsion with ultrasonic waves continuously in order to
repress the production of the hydrate. These controls are
optionally taken as occasion demands, and thus it is not always
necessitated.
[0014] As the guest molecules in the method for production of the
gas hydrate according to the present invention, any molecules
capable of producing hydrate can be utilized. Among them, CO.sub.2
is particularly desirable.
[0015] The method for substitution of gas hydrate according to the
present invention is characterized in that, to voids in a layer
where hydrate of first guest molecules exists, an emulsion in which
a liquid of second guest molecules is dispersed in water as
particles having a size of less than the size of the voids is
injected, wherein the second guest molecules can form hydrate under
a higher temperature and lower pressure condition as compared with
the temperature and pressure condition under which the first guest
molecules forms the hydrate; and thereby the hydrate of the first
guest molecules is decomposed by heat which is generated when the
hydrate of the second guest molecules is produced.
[0016] In this substitution method of gas hydrate, as is the case
with the production method of gas hydrate mentioned above, it is
possible that the mixing ratio of the liquid of the second guest
molecules and water in the emulsion is varied in order to control
the heating value per unit volume of emulsion. Further, it is also
possible that the size of the liquid minute particles of second
guest molecules in emulsion is varied in order to control the
production rate of hydrate.
[0017] In addition, when irradiating the emulsion with ultrasonic
waves in the early stage of substitution, the interfaces between
the minute particles of the second guest particles and water are
activated. When irradiating the emulsion with ultrasonic waves, the
production of the hydrate of the second guest molecules is
repressed during the irradiation.
[0018] Further, in the method for substitution of gas hydrate
according to the present invention, the progress for decomposition
of the hydrate of the first guest molecules and the progress for
production of the hydrate of the second guest molecules are
estimated by at least one or more of the change in temperature of
the layer, the change in passing speed of ultrasonic waves through
the layer, and the change in permeability of the emulsion into the
voids.
[0019] In addition, in the method for substitution of gas hydrate
according to the present invention, it is preferable to use
CH.sub.4 as the first guest molecules, and CO.sub.2 as the second
guest molecules, respectively.
[0020] The method for mining of gas hydrate according to the
present invention is characterized in that, to voids in a layer
where CH.sub.4 hydrate exists, an emulsion in which a liquid
CO.sub.2 is dispersed in water as particles having a size of less
than the size of the voids is injected, wherein the emulsion is
used as a heating agent for decomposing the CH.sub.4 hydrate
existing in the voids.
[0021] Further, the method for mining of gas hydrate according to
the present invention is characterized in that, to voids in a layer
which is rested on a CH.sub.4 hydrate layer and is under the
temperature and pressure condition that CO.sub.2 can forms hydrate,
an emulsion in which a liquid CO.sub.2 is dispersed in water as
particles having a size of less than the size of the voids is
injected in order to form a seal layer of CO.sub.2 hydrate; and
then the emulsion is injected to voids in the CH.sub.4 hydrate
layer so that CO.sub.2 hydrate is produced while decomposing the
CH.sub.4 hydrate existed in the voids by heat of reaction in the
CO.sub.2 hydrate production, thus the CH.sub.4 hydrate is
substituted with the CO.sub.2 hydrate while recovering CH.sub.4
gas.
[0022] Alternatively, the method for mining of gas hydrate
according to the present invention is characterized in that, to
voids in a layer which is rested on a CH.sub.4 hydrate layer and is
under the temperature and pressure condition that CO.sub.2 can
forms hydrate, an emulsion in which a liquid CO.sub.2 is dispersed
in water as particles having a size of less than the size of the
voids is injected in order to form a seal layer of CO.sub.2
hydrate; and the emulsion is injected to voids in a layer which is
rested under the CH.sub.4 hydrate layer in order to produce
CO.sub.2 hydrate and to cause the temperature of this layer to rise
by heat of reaction in the CO.sub.2 hydrate production, by which
risen temperature of the CH.sub.4 hydrate existing in the CH.sub.4
hydrate layer which is rested on this layer is decomposed from the
lower side; and the CH.sub.4 gas is collected by the seal layer in
order to recover the CH.sub.4 gas to the ground, while the strength
of the layer after mining the CH.sub.4 hydrate is restored by
injecting the emulsion into the layer so as to form CO.sub.2
hydrate therein.
EFFECT OF THE INVENTION
[0023] In accordance with the method for production of gas hydrate
of the present invention, since the liquid of the guest molecules
which is injected into the layer is in the emulsion state where the
liquid of guest molecules is dispersed in water as particles having
a size of less than the size of the voids in the layer, like water,
the liquid of the guest molecules can enter into the void easily
without disturbance while displacing water or seawater filled in
the void in the layer from the void, or can disperse in the water
or seawater, and thus it can be distributed uniformly in the layer
while maintaining the emulsion state where the minute particles of
the guest molecules are admixed with the seawater. In addition,
since the liquid of guest molecules is made into the emulsion state
in advance of it's injection into the layer, it is possible to
disperse water and the guest molecules with a ratio suitable for
the production of hydrate, and thus, it is possible to produce the
hydrate uniformly and efficiently.
[0024] Further, since the contacting area between the liquid of
guest molecules and water can be enlarged dramatically by preparing
the minute particles, it is possible to accelerate the reaction
rate and thus it is possible to accelerate the production of
hydrate. In addition, since the hydrate can be produced quickly, it
is possible to fixate a large amount of guest molecules into the
layer. Furthermore, since the time required for the production of
the hydrate can be shortened and the hydrate can be produced
quickly, it is possible to repress the migration and diffusion of
the liquid of the guest molecules which are caused by the flow of
groundwater or the buoyancy of the liquid.
[0025] Further, in accordance with the method for production of gas
hydrate of the present invention, it is possible to control the
temperature of the layer to the temperature at which the gas
hydrate can be produced, when the mixing ratio of the liquid of the
guest molecules and water is varied so as to control the heating
value per unit volume of emulsion, or when the temperature of water
as the dispersion medium is varied so as to change the temperature
of the emulsion in itself. In this case, there is no fear that the
hydrate becomes unstable due to the temperature rising of the layer
associated with the production of gas hydrate, and there is no need
for preparing any temperature reducing mechanisms.
[0026] Further, in accordance with the method for production of gas
hydrate of the present invention, it is possible to control the
production rate of the hydrate, when the specific surface area of
the minute particles of the liquid of the guest molecules in the
emulsion is varied by varying the size of the minute particle.
Therefore, only by regulating the size of the minute particles of
the liquid of the guest molecules, it is possible to control the
production rate of the hydrate.
[0027] Further, in the method for production of gas hydrate of the
present invention, it is also possible to accelerate the reaction
rate and to accelerate the production of the hydrate, when the
interfaces between the minute particles of the liquid of the guest
particles and water are activated by irradiating them with the
ultrasonic waves.
[0028] Further, in accordance with the present invention, since the
production of the hydrate can be repressed by irradiating the
emulsion with the ultrasonic waves continuously and thus causing
the minute particles and water to vibrate, it is possible to
control the timing of initiating the production of the hydrate by
regulating the irradiation time of the ultrasonic waves.
[0029] In addition, in the method for production of gas hydrate of
the present invention, it is also possible to fixate a great amount
of CO.sub.2 which is the cause of global warming in the layer, when
CO.sub.2 is used as the guest molecules and the hydrate thereof is
produced in the voids of the layer.
[0030] In accordance with the method for substitution of gas
hydrate of the present invention, it is possible to substitute the
gas hydrate without causing weakening or collapse of the layer.
Because, only by injecting the emulsion where the minute particles
of the second guest molecules are admixed with seawater into the
layer where the hydrate of the first guest molecules exists, the
decomposition of the gas hydrate in which the first guest molecules
have been included can be progressed at a rapid reaction rate while
a gas hydrate in which the second guest molecules are included is
produced. Therefore, even if a submarine landslide on a large scale
will happen due to an earthquake or the like during the operation
for the gas hydrate substitution, there is not very much risks
about the leak of the gas of the second guest molecules which is
injected into the layer, and about the leak of the gas of the first
guest molecules which is produced by the decomposition, into the
atmosphere, as well as about the release of the gas hydrate into
the atmosphere as a result of ascending the gas hydrate with the
buoyancy and then allowing it to gasify. In addition, since the
reaction area necessitated for accelerating the chemical reaction
is enlarged by making the second guest molecules into the minute
particles and thus the heat necessitated for decomposing the gas
hydrate can be supplied efficiently by the heat on the production
of the other gas hydrate, it is possible to repress the generation
of CO.sub.2 for obtaining the heat.
[0031] Further, in accordance with the method for substitution of
gas hydrate of the present invention, it is possible to control the
temperature rising of the layer in order to regulate the
decomposition rate of the gas hydrate to be substituted, when the
mixing ratio of the liquid of the guest molecules and water in the
emulsion is varied so as to control the heating value per unit
volume of emulsion, or when the temperature of water as the
dispersion medium is varied so as to change the temperature of the
emulsion in itself.
[0032] Further, in accordance with the method for substitution of
gas hydrate of the present invention, it is possible to control the
production rate of the hydrate of the second guest molecules, when
the specific surface area of the minute particles of the liquid of
the guest molecules in the emulsion is varied by varying the size
of the minute particle.
[0033] Further, in the method for substitution of gas hydrate of
the present invention, it is also possible to accelerate the
reaction rate and to accelerate the production of the hydrate of
the second guest molecules, when the interfaces between the minute
particles of the liquid of the second guest particles and water are
activated by irradiating them with the ultrasonic waves in the
early stage of substitution. Further, since the production of the
hydrate can be repressed by irradiating the emulsion with the
ultrasonic waves continuously and thus causing the minute particles
and water to vibrate, it is possible to control the timing of
initiating the production of the hydrate by regulating the
irradiation time of the ultrasonic waves. By these controls for the
hydrate production, it is possible to control the temperature
rising of the layer and to control the decomposition rate of the
gas hydrate.
[0034] In addition, in the method for substitution of gas hydrate
of the present invention, since the progress for decomposition of
the hydrate of the first guest molecules and the progress for
production of the hydrate of the second guest molecules can be
estimated on the basis of at least one or more of the change in
temperature of the layer, the change in passing speed of ultrasonic
waves through the layer, and the change in permeability of the
emulsion into the voids, it is possible to regulate the production
rate or decomposition rate of gas hydrate in accordance with the
estimation.
[0035] Further, in the method for substitution of gas hydrate of
the present invention, it is possible to fixate a great amount of
CO.sub.2 on the ground which is the cause of global warming, in the
form of a stable hydrate into the layer, while collecting the
CH.sub.4 in marine sediments by utilizing the heat of reaction for
the hydrate production, when the first guest molecules are CH.sub.4
and the second guest molecules are CO.sub.2.
[0036] In accordance with the method for mining of gas hydrate of
the present invention, it is possible to fixate a great amount of
CO.sub.2 on the ground which is the cause of global warming, in the
form of a stable hydrate into the layer at a high reaction rate,
while collecting the CH.sub.4 in marine sediments by utilizing the
heat of reaction for the hydrate production, when the first guest
molecules are CH.sub.4 and the second guest molecules are CO.sub.2.
Further, since the mining of the CH.sub.4 hydrate is progressed
while substituting the CH.sub.4 hydrate with the CO.sub.2 hydrate,
there is no fear of causing the weakening or collapse of the layer.
In addition, since the energy for decomposing the CH.sub.4 hydrate,
wherein the decomposition of the CH.sub.4 hydrate is necessitated
for the mining of the CH.sub.4 hydrate, is obtained by using the
CO.sub.2, which is fixate as waste in the layer, as a heating
agent, it is possible to give the additional value to the waste
CO.sub.2 and to utilize the energy effectively.
[0037] Further, in accordance with the method for mining of gas
hydrate of the present invention, since the seal layer of CO.sub.2
hydrate is formed in the layer which is rested on the CH.sub.4
hydrate layer as the target of mining, by the production method for
gas hydrate of the present invention, the solid phases in the layer
are mutually adjoined owing to the fact that the voids in the layer
are filled with the CO.sub.2 hydrate, and become stable. Therefore,
even if a submarine landslide on a large scale will happen due to
an earthquake or the like, there is not very much risks about the
leak of CH.sub.4 gas, which is produced by decomposition of the
CH.sub.4 hydrate, into the atmosphere, and about the release of the
CH.sub.4 hydrate into the atmosphere as a result of ascending the
CH.sub.4 hydrate with the buoyancy, wherein the density of CH.sub.4
hydrate is lower than that of seawater, and then allowing it to
gasify. This point is particularly useful since the ocean
sedimentary layer where the CH.sub.4 hydrate is deposited is
accumulated in sand layer. In addition, it is possible to fixate
the CO.sub.2 as a stable hydrate in both of the CH.sub.4 hydrate
layer and the seal layer.
[0038] Further, in accordance with the method for mining of gas
hydrate of the present invention, since the seal layer of CO.sub.2
hydrate is formed in the layer which is rested on the CH.sub.4
hydrate layer as the target of mining, and the heating layer of
CO.sub.2 hydrate is formed in the layer which is rested under the
CH.sub.4 hydrate layer, by using the production method for gas
hydrate of the present invention, it is possible to mine and
recover the CH.sub.4 hydrate safety without causing leak of methane
gas, and also possible to fixate a large amount of CO.sub.2 as a
stable hydrate into three layers, i.e., the seal layer, the layer
which functions as the heating source, and the layer from which the
CH.sub.4 hydrate is mined.
BRIEF DESCRIPTION OF DRAWINGS
[0039] [FIG. 1] is a schematic diagram which illustrates an
embodiment of the method for substitution of gas hydrate according
to the present invention.
[0040] [FIG. 2] is a diagram which illustrates a state of producing
CO.sub.2 hydrate and decomposing CH.sub.4 hydrate when liquid
CO.sub.2 4 is injected into voids under the condition that the
liquid CO.sub.2 4 has been divided into minute particles.
[0041] [FIG. 3] is a schematic diagram which illustrates a state of
substitution of CH.sub.4 hydrate with CO.sub.2 hydrate.
[0042] [FIG. 4] is a schematic diagram which illustrates upper
portions of an injection well.
[0043] [FIG. 5] is a schematic diagram which illustrates lower
portions of an injection well.
[0044] [FIG. 6] is a sectional diagram of submarine ground which
illustrates a state of substitution of CH.sub.4 hydrate with
CO.sub.2 hydrate.
[0045] [FIG. 7] is a chart showing phase equilibrium of CH.sub.4
hydrate and CO.sub.2 hydrate.
[0046] [FIG. 8] shows changes in the substitution of CH.sub.4
hydrate with CO.sub.2 hydrate along the course of time, wherein (A)
is a chart showing changes in constituents of CH.sub.4 hydrate
layer, and (B) is a chart showing change in temperature of voids in
the CH.sub.4 hydrate layer, change in the rate of ultrasonic waves,
and change in permeability of emulsion.
[0047] [FIG. 9] is a schematic diagram which illustrates an
embodiment of the method for production of gas hydrate according to
the present invention.
[0048] [FIG. 10] is a diagram which illustrates a state of
producing CO.sub.2 hydrate and decomposing CH.sub.4 hydrate when
liquid CO.sub.2 4 is injected into voids under the condition that
the liquid CO.sub.2 4 are not divided into minute particles.
[0049] [FIG. 11] is a schematic diagram which illustrates an
embodiment of the method for mining of gas hydrate with showing an
example for mining of CH.sub.4 hydrate.
[0050] [FIG. 12] is a graph which shows a distribution of particle
sizes at a sedimentary layer in Nankai trough.
[0051] [FIG. 13] is a schematic diagram of an experimental
device.
[0052] [FIG. 14] is a microscopic photograph of finely divided
liquid CO.sub.2 in water.
[0053] [FIG. 15] is a microscopic photograph for comparing finely
divided liquid CO.sub.2 in water with Toyoura sand.
[0054] [FIG. 16] is a graph which shows relations between particle
size and percentage of penetrated weight with respect to the finely
divided liquid CO.sub.2 in water and Toyoura sand.
[0055] [FIG. 17] is a schematic diagram which shows positions for
measuring temperature in a pressure vessel for producing CO.sub.2
hydrate.
[0056] [FIG. 18] is a graph which shows a result of an experiment
for production of CO.sub.2 hydrate, wherein (A) shows the
temperature change from the start time to the end time in the
experiment, and (B) shows the temperature change before and after
the production of CO.sub.2 hydrate in a magnified scale.
[0057] [FIG. 19] is a graph which shows a result of an experiment
for production of CO.sub.2 hydrate as Control 1, wherein gas
hydrate is produced from liquid CO.sub.2.
DESCRIPTION OF NUMERALS
[0058] 1 CH.sub.4 hydrate (hydrate of the first guest molecules)
[0059] 2 Layer where CH.sub.4 hydrate is produced [0060] 3 Void
[0061] 4 Liquid CO.sub.2 (liquid of the second guest molecules)
[0062] 5 CO.sub.2-- water emulsion [0063] 6 CO.sub.2 hydrate
(hydrate of the second guest molecules) [0064] 23 Minute particles
of liquid CO.sub.2 (liquid minute particles of the second guest
molecules)
BEST MODE FOR CARRYING OUT THE INVENTION
[0065] Hereinafter, the constitution of the present invention will
be described in detail with reference to best modes illustrated in
the drawings.
[0066] In FIGS. 1-6, an embodiment of the method for substitution
of hydrate in the layer, which utilizes the method for production
of gas hydrate according to the present invention, is illustrated.
In the description of this embodiment, the method for production of
gas hydrate will be also explained. The method for substitution of
gas hydrate according to the present invention is the method
wherein the production of a gas hydrate is artificially promoted in
a layer, which brings the layer into a risen temperature condition,
and thereby a natural gas hydrate which has been produced in the
layer is decomposed, thus the guest molecules are replaced; and
wherein, to voids 3 in a layer 2 where hydrate 1 of first guest
molecules exists, a liquid 4 of second guest molecules is injected
in a form of emulsion 5 in which the liquid 4 of the second guest
molecules is dispersed as particles having a size of less than the
size of the voids 3 in a dispersion medium 24, wherein the second
guest molecules can form hydrate under a higher temperature and
lower pressure condition as compared with the temperature and
pressure condition under which the first guest molecules forms the
hydrate, and thereby the hydrate 1 of the first guest molecules is
decomposed by heat of reaction which is generated when the hydrate
6 of the second guest molecules is produced. Incidentally, the
numeral 25 in FIG. 2 denotes sand particles in the layer 2. The
layer 2 may be, for instance, a submarine layer, and as the
dispersion medium 24 of the emulsion, water or seawater which can
form a crystal for entrapping the guest molecule is used. Herein,
the voids in the layer are spaces between solid phases (sand
particles, CO.sub.2 hydrate, CH.sub.4 hydrate), and substantially
mean regions which are occupied by liquid phase (liquid CO.sub.2,
water, seawater) and gas phase (methane gas). That is, the liquid
of the guest molecules is spouted as the emulsion where the liquid
of the guest molecules is dispersed as particles having a size of
less than the size of the spaces between the solid phases in the
layer where the gas hydrate is formed.
[0067] The first guest molecules in the method for substitution of
gas hydrate according to this embodiment may be, for example,
CH.sub.4, and the hydrate 1 of the first guest molecules may be
CH.sub.4 hydrate. Further, the second guest molecules may be, for
example, CO.sub.2, the hydrate 6 of the second guest molecules may
be CO.sub.2 hydrate, and the liquid 4 of the second guest molecules
may be liquid CO.sub.2.
[0068] FIG. 7 is a chart showing phase equilibrium of CH.sub.4
hydrate and CO.sub.2 hydrate. The region blow the curve A is the
stable region of CO.sub.2 hydrate 6, the region blow the curve B is
the stable region of CH.sub.4 hydrate 1, the region at the left of
the curve C is the region where H.sub.2O becomes solid, and the
region at the right of the curve C is the region where H.sub.2O
becomes liquid. As it is clear from FIG. 7, assuming that the
pressures are the same, the temperature at which the CO.sub.2
hydrate 6 exists in stable is higher than the temperature at which
the CH.sub.4 hydrate 1 exists in stable. Further, assuming that the
temperatures are the same, the pressure under which the CO.sub.2
hydrate 6 exists in stable is lower than the pressure under which
the CH.sub.4 hydrate 1 exists in stable. That is, the temperature
and pressure under which the CO.sub.2 hydrate 6 exists in stable is
higher temperature and lower pressure as compared with the
temperature and pressure under which the CH.sub.4 hydrate 1 exists
in stable. The region surrounded by curves A, B and C is the region
which temperature and pressure conditions permit causing both the
production of CO.sub.2 hydrate 6 and the decomposition of CH.sub.4
hydrate 1 concurrently. Thus, by utilizing this region, to
substitute the CO.sub.2 hydrate 6 for the CH.sub.4 hydrate 1 is
performed. By substituting the CO.sub.2 hydrate 6 for the CH.sub.4
hydrate, it becomes possible to mine CH.sub.4 while fixating
CO.sub.2.
[0069] In the submarine ground, the places where the CH.sub.4
hydrate is accumulated are sand layer, and thus, the target for
mining the CH.sub.4 hydrate is set to such an accumulated place.
With recent studies, it has been found that CH.sub.4 hydrate exists
in spaces which constitute a three-dimensional network structure
occupying about 50% of the sand layer, and the CH.sub.4 hydrate is,
at the most, of 60% of the spaces. Thus, the following will be
explained about the case that the submarine layer 2 is the target
layer for mining of the CH.sub.4 hydrate and for fixating the
CO.sub.2 hydrate. The lower end of an injection well 7 and the
lower end of a production well 8 reach the layer 2 where CH.sub.4
hydrate has been produced. On the sea, a platform 9 is provided,
and the injection well 7 and the production well 8 are elongated
downward from the platform 9 to the bottom of the sea. The upper
end of the production well 8 is connected to a pump which is not
shown in this figure, and thus it can pump CH.sub.4 gas up together
with seawater 24 which has filled the spaces in the layer 2. The
CH.sub.4 gas pumped up by the production well 8 may be used, for
instance, for electric power generation at thermal power plant 26,
after separating it from the seawater 24.
[0070] As shown in FIG. 4, the injection well 7 has a double pipe
constitution where an inner pipe 11 is placed inside an outer pipe
10. The upper end of the inner pipe 11 is connected to a liquid
CO.sub.2 tank 12, and a pathway through which liquid CO.sub.2 4
flows is formed in the inner pipe 11. The liquid CO.sub.2 4
reserved in the liquid CO.sub.2 tank 12 is prepared by collecting
CO.sub.2 discharged from the thermal power plant 26, a steelworks,
or a cement plant, or the like, and liquefying the collected
CO.sub.2. Further, as shown in FIG. 5, at the end of the inner pipe
11, spray nozzles 13, through which the liquid CO.sub.2 is sprayed
as minute particles 23 which are smaller than the voids 3 in the
layer 2 into the pathway which is surrounded with the outer pipe
10, are provided. By producing a high speed flows within the
nozzles 13, and thus by giving shearing and collision effects, the
liquid CO.sub.2 can be divided into the minute particles. Although
the method for atomization of a liquid by using nozzle, per se, is
a generally known technique which is also applied in sprayers,
however, when the pressure difference between front and rear of the
nozzle 13 is set to 1 MPa--some tens MPa so that the flow rate of
the liquid CO.sub.2 4 in the nozzle 13 reaches about the speed of
sound, it is possible to prepare minute particles 23 of the liquid
CO.sub.2 4 sprayed from the nozzle 13 in sizes of under .mu.m
order. Herein, since it is necessitated that the mean particle size
of the minute particles 23 of liquid CO.sub.2 on the spraying
should be smaller than the voids in the layer where the gas hydrate
is produced, i.e., the voids between the solid phases, for
instance, it is preferable to be from about some .mu.m to about 30
.mu.m. When satisfying this condition, it is considered that the
minute particles come to be amply smaller than the voids in the
layer where the gas hydrate is produced. Incidentally, at a
position near the liquid CO.sub.2 tank 12, the inner pipe 11 is
equipped with a pressure gauge 15 for measuring the pressure of the
liquid CO.sub.2 4.
[0071] The upper end of the outer pipe 10 is connected to an outlet
of a pump 14 which pumps seawater 24 up from the ocean 31 and
discharges it, and a pathway through which the seawater 24 flows is
formed at the space between the outer pipe 10 and the inner pipe
11. When the minute particle 23 of the liquid CO.sub.2 4 are
sprayed into the flow of the seawater 24 which passes through the
space between the outer pipe 10 and the inner pipe 11, it is
possible to prepare a CO.sub.2-- water emulsion 5 where the liquid
CO.sub.2 4 is dispersed, as minute particles having a size of less
than the voids 3, in the seawater 24, just before the emulsion is
jetted into the layer 2. The pumping up of the seawater 24 from the
ocean 31 can be performed from any depths until reaching the sea
bottom, by adjusting the length of a suction pipe 14a.
Incidentally, the outer pipe 10 may be, for instance, a drill rod,
and it has many injection ports 10a for injecting uniformly the
prepared CO.sub.2-- water emulsion 5 into the layer 2, on the
peripheral surface. Injection port 10a is positioned ahead of the
end of the inner pipe 11 where the splay nozzles 13 are
provided.
[0072] Thereby, in the injection well 7, the weight ratio of water
and CO.sub.2 in the emulsion can be adjusted to a preferable value
in accordance with the purpose of producing hydrate, before the
emulsion is injected into the layer 2. For instance, the mixing
ratio of water and CO.sub.2 can be adjusted in accordance with the
purpose of producing hydrate, for instance, a purpose that is to
fixate guest molecules stably by producing hydrate in the targeted
layer 2, a purpose that is to substitute supplied guest molecules
for other guest molecules of the gas hydrate which exists in the
layer, a purpose is to utilize the heat of reaction obtained when
the hydrate is produced as a heat source for mining a natural
resource which exists in the form of hydrate in the layer, and so
on. For example, as in this embodiment, in the case that CO.sub.2
is fixated in the form of hydrate in the layer 2 where CH.sub.4
hydrate has been accumulated, while the CH.sub.4 hydrate is
decomposed into water and CH.sub.4 in order to collect them,
thereby the CH.sub.4 hydrate is mined by substituting the CO.sub.2
hydrate for the CH.sub.4 hydrate in the layer, it is preferable to
adjust the weight ratio of water and CO.sub.2 to a value suitable
for the production and stability of CO.sub.2 hydrate. Further, when
regulating the temperature of the seawater or water used as
dispersion medium of the emulsion 5, or the temperature of the
liquid CO.sub.2, it is possible to injected the emulsion with
giving a temperature condition which is profitable to produce the
hydrate and maintain it stably against the temperature condition of
the layer where the production of gas hydrate is intended and the
temperature rising condition of the layer. For instance, when
varying the depth for collecting the seawater 24, it is possible to
obtain water or seawater at a desired temperature with ease.
[0073] The emulsion 5 jetted from the injection well 7 enters into
voids 3 of the CH.sub.4 hydrate layer 2, while displacing seawater
which have been filled in the voids, and thus the liquid CO.sub.2
and the seawater 24 can reach every part of the voids 3 with a
uniform ratio. In the voids, CH.sub.4 hydrate is in existence
stably. Thus, the temperature and pressure condition of the voids 3
is also to be a temperature and pressure condition where the
CO.sub.2 hydrate can exist stably. Therefore, CO.sub.2 hydrate 6 is
produced from the emulsion 5 entered into the voids.
[0074] The production of hydrate is an exothermic reaction, whereas
the decomposition of hydrate is an endothermic reaction. Due to the
heat emitted when the CO.sub.2 hydrate 6 is produced, the
temperature of the layer 2 including surrounding solid phases and
liquid phases rises, and CH.sub.4 hydrate is decomposed. For
example, assuming that the temperature moves upward from the point
P1 to the point P2 in FIG. 7, although the voids 3 belong to the
CO.sub.2 stable region in FIG. 7, the voids 3 deviate from the
CH.sub.4 stable region. Therefore, the CH.sub.4 hydrate in the
voids 3 is decomposed, whereas the CO.sub.2 hydrate 6 exists
stably. Thus, with respect to the hydrate capable of existing in
the voids 3, the CH.sub.4 hydrate is replaced with the CO.sub.2
hydrate. Incidentally, with respect to the substitution in the
voids 3, although the main phenomenon thereof is that the CH4
hydrate 1 is decomposed following the progress of the production of
the CO.sub.2 hydrate, a phenomenon where the CH.sub.4 that is the
guest molecules of CH.sub.4 hydrate 1 is replaced with CO.sub.2
without causing the decomposition of the CH.sub.4 hydrate 1 also
occurs in a part.
[0075] Since the heat emitted when the CO.sub.2 hydrate 6 is
produced is absorbed on the decomposition of the CH.sub.4 hydrate
1, the temperature of the voids 3, by extension, the temperature of
the layer 2, does not rise exceed the temperature at which the
CO.sub.2 hydrate can be produced and can exist stably. Thus, the
produced CO.sub.2 hydrate 6 exists stably.
[0076] By the decomposition of the CH.sub.4 hydrate 1, CH.sub.4 gas
27 is generated. The CH.sub.4 gas 27 forms bubbles, and they float
in the seawater 24 which flows in the void 3. Further, a part of
the CH.sub.4 gas 27 is dissolved in groundwater 24. On the other
hand, since the emulsion 5 is discharged from the injection well 7
and the groundwater 24 is pumped up by the production well 8, a
flow of the groundwater 24 from the injection well 7 to the
production well 8 is formed in the voids 3. Thus, both of the
bubbles of the generated CH.sub.4 gas 27 and the CH.sub.4 gas 27
dissolved in the seawater 24 are collected along with the seawater
24 by the production well 8.
[0077] As mentioned above, when the hydrate is produced by
injecting CO.sub.2 into the submarine layer, and the CH.sub.4
hydrate 1 in the submarine layer which is an effectual resource is
decomposed due to the temperature rising of the layer 2 which is
induced by the heat of reaction which is emitted when the CO.sub.2
hydrate 6 is produced, and thereby the CH.sub.4 hydrate 1 is
replaced with the CO.sub.2 hydrate; it is possible to progress the
fixation of CO.sub.2 and the mining of the CH.sub.4 hydrate 1, as
well as the recovery and stabilization of the strength of the
layer, simultaneously. Further, it is also possible to use the
guest molecules simply as a heating agent, such as CO.sub.2 in this
embodiment, which is to be fixated through the production of
hydrate.
[0078] Since the liquid CO.sub.2 in the emulsion 5 is brought into
the form of minute particles 23 which are smaller than the voids 3
in the layer 2, the liquid CO.sub.2 can enter into the voids 3 in
the layer 2 with ease and without impediments to it's movement,
like water, and thus it can be dispersed within the voids with a
uniform distribution. Therefore, it is possible to disperse the
liquid CO.sub.2 uniformly over a broader region of the voids 3 in
the layer 2, with a water --CO.sub.2 ratio which is suitable or
nearly suitable to the hydrate production, and thus it is possible
to produce the CO.sub.2 hydrate uniformly over a broad region.
[0079] Further, since the liquid CO.sub.2 4 is brought into the
form of minute particles, the contacting area between the liquid
CO.sub.2 4 and the seawater 24 becomes large. For instance,
assuming that the particle of liquid CO.sub.2 is a sphere, when its
radius becomes one-tenth, the number of particles per unit volume,
the surface area of each individual particle 23, and the total of
the surface areas per unit volume will become 1000 times,
one-hundredth, and ten times, respectively. For instance, assuming
that the surface area of the minute particle 23 at when its radius
is 1 mm is a criterion, when the diameter of the minute particles
23 is set to 0.01 mm or 0.001 mm, the total of the surface areas
per unit volume will become 100 times, or 1000 times, respectively.
As described above, since it is possible to enhance the contacting
area between the liquid CO.sub.2 4 and the seawater 24, it becomes
possible to accelerate the reaction rate so that the CO.sub.2
hydrate is promptly produced.
[0080] For reference purposes, in FIG. 10, a state when liquid
CO.sub.2 4 is injected into voids 3 in the layer 2 under the
condition that the liquid CO.sub.2 are not divided into minute
particles and it is in it's intact state of almost 100%
concentration is shown. In this case, since the liquid CO.sub.2
enters into the voids while the liquid CO.sub.2 puts the seawater
24 filled in the voids away from the void, the liquid CO.sub.2
makes contact with the seawater 24 only on the border between the
liquid CO.sub.2 and seawater 24, and only one of the liquid
CO.sub.2 and seawater 24 exists inside the border. Therefore, it is
hardly possible to distribute the water and liquid CO.sub.2
uniformly with a ratio which is suitable to the hydrate production
in the voids 3.
[0081] Further, in accordance with the present invention, since it
is possible to accelerate the production rate of the gas hydrate,
the present invention is useful for not only the substitution of
one hydrate for another hydrate and the mining of the resource
hydrate, but also for the fixation and storage of guest molecules
in hydrate form into a layer. For instance, the present invention
is suitable for a technique for fixation of CO.sub.2 which has been
discharged in large amount.
[0082] Further, in the present invention, since the liquid CO.sub.2
is brought into the form of minute particles which are smaller than
the voids in the layer 2 in advance and thus it is supplied in
emulsion form, it becomes possible to control the heating value per
unit volume of emulsion 5 when the mixing ratio of the liquid
CO.sub.2 4 and water 24 in the emulsion which is injected into the
voids 3 of the CH.sub.4 hydrate layer 2 from the injection well 7.
For example, by regulating the ratio of the liquid CO.sub.2 4 flow
rate and the seawater 24 flow rate in the injection well 7, the
mixing ratio of the liquid CO.sub.2 4 and water 24 can be varied,
and thus it becomes possible to control the heating value per unit
volume of emulsion 5.
[0083] The ratio of the number of guest molecule and the number of
water molecule for constituting a hydrate depends on the kind of
guest molecule. When the mixing ratio of the liquid CO.sub.2 4 and
water 24 in the emulsion 5 approaches the ratio of the number of
CO.sub.2 molecule and the number of water molecule for constituting
the CO.sub.2 hydrate, the quantity of the hydrate production per
unit amount of the emulsion 5 increases and the heating value also
increases. Conversely, when the mixing ratio of the liquid CO.sub.2
4 and water 24 in the emulsion 5 is away from the ratio of the
number of CO.sub.2 molecule and the number of water molecule for
constituting the CO.sub.2 hydrate, the quantity of the hydrate
production per unit amount of the emulsion 5 decreases and the
heating value also decreases. Therefore, by varying the mixing
ratio of the liquid CO.sub.2 4 and water 24 in the emulsion 5, the
heating value per unit volume of emulsion 5 on the production of
the CO.sub.2 hydrate can be controlled. Further, by controlling the
heating value per unit volume of emulsion 5 on the production of
the CO.sub.2 hydrate, the temperature rising of the layer 2 can be
regulated. Owing to this temperature regulation of the layer 2, it
becomes possible to keep the temperature of the layer 2 to the
temperature capable of producing the gas hydrate, or to regulate
the decomposition rate of the hydrate to be replaced or to be
mined, such as CH.sub.4 hydrate 1. Of course, in the cases of the
replacement of CH.sub.4 hydrate by the CO.sub.2 hydrate production
and the mining of CH.sub.4 hydrate by the CO.sub.2 hydrate
production, since the heating value and the endothermic heating
value of both hydrates can balance each other out, the temperature
regulation is not necessitated.
[0084] Further, in the present invention, the production rate of
the CO.sub.2 hydrate is controlled by varying the particle size of
the minute particles 23 of the liquid CO.sub.2 4 in the emulsion 5
which is to be injected into the voids 3 of the CH.sub.4 hydrate
layer 2 from the injection well 7. For instance, by replacing a
nozzle 13 of the injection well 3 to another one, the particle size
of the minute particles 23 of the liquid CO.sub.2 in the emulsion 5
can be varied, and thus the production rate of the CO.sub.2 hydrate
can be controlled.
[0085] When the particle size of the minute particles 23 of the
liquid CO.sub.2 in the emulsion 5 becomes small, the surface area
of the liquid CO.sub.2 per unit volume of the liquid CO.sub.2, in
other words, the contacting area between the liquid CO.sub.2 and
the seawater 24 increases, and thus the production rate of the
CO.sub.2 hydrate increases. Conversely, When the particle size of
the minute particles 23 of the liquid CO.sub.2 in the emulsion 5
becomes large, the contacting area between the liquid CO.sub.2 and
the seawater 24 decreases, and thus the production rate of the
CO.sub.2 hydrate decreases. Thus, by varying the particle size of
the minute particles 23 of the liquid CO.sub.2, the production rate
of the CO.sub.2 hydrate can be controlled.
[0086] Furthermore, in this invention, by irradiating the emulsion
5 with the ultrasonic waves in the early stage of the substitution
of the hydrate, the interfaces between the minute particles of the
liquid of the second guest particles and water are activated, and
thus, CO.sub.2 as the guest molecules can be brought into condition
to form hydrate with ease. With respect to this point, if
undergoing the ultrasonic waves' irradiation continuously, the
minute particles of the liquid CO.sub.2 are vibrate and thus they
can not form the hydrate. Once the irradiation is stopped, however,
the production of the hydrate is initiated. Thus, by controlling
the irradiation time of the ultrasonic wave, the initiation timing
for the production of the CO.sub.2 hydrate can be controlled. For
instance, although it is not shown in the drawings, it is possible
to incorporate two kinds of ultrasonic waves generation devices 55,
56 into the end of the inner pipe 11, wherein the first ultrasonic
waves generation devices 55 is used for activating the interfaces
between CO.sub.2 and water in the CO.sub.2-- water emulsion
existing in the outer pipe 10 and thus accelerating the production
of the hydrate, while the second ultrasonic waves generation
devices 56 is used for giving ultrasonic waves continuously toward
the layer 2 so as to vibrate the layer 2 continuously, and to
repress the production of the CO.sub.2 hydrate. Incidentally, as
the means for irradiating the minute particles 23 of the liquid
CO.sub.2 with the ultrasonic waves, for example, it is also
possible to use an ultrasonic generating and receiving device 16
which is settled at the CH.sub.4 hydrate layer 2 for measuring the
ultrasonic wave speed.
[0087] Still further, according to the present invention, since the
liquid CO.sub.2 as the guest molecules can be in the emulsion form
where the liquid CO.sub.2 is dispersed in water with an uniform
ratio necessitated for the production of the hydrate, in order to
inject it into the layer, the liquid CO.sub.2 and the seawater 24
can be distributed throughout the voids 3, and therefore, the
progress for decomposition of the CH.sub.4 hydrate 1 and the
progress for production of the CO.sub.2 hydrate 6 can be estimated
on the basis of the change in temperature of the layer 2, the
change in passing speed of the ultrasonic waves through the layer,
and the change in permeability of the emulsion 5 into the voids
3.
[0088] The temperature of the layer 2 where the CH.sub.4 hydrate
has been produced takes changes due to the exothermic heat on the
production of the CO.sub.2 hydrate 6 and the endothermic heat on
the decomposition of the CH.sub.4 hydrate 1. The passing speed of
the ultrasonic waves through the layer 2 is varied by the kind,
amount, phase (gas phase, liquid phase, or solid phase), etc., of
the substance existing in the voids 3. The permeability of the
emulsion 5 into the voids 3 in the layer 2 is also varied by the
kind, amount, phase (gas phase, liquid phase, or solid phase),
etc., of the substance existing in the voids 3. Thus, the state of
substitution of CO.sub.2 hydrate 6 for the CH.sub.4 hydrate 1 can
be estimated by monitoring the change in temperature of the voids
3, the change in passing speed of ultrasonic waves through the
voids 3, and the change in permeability of the emulsion 5 into the
voids 3.
[0089] Changes in the replacement of CH.sub.4 hydrate 1 with
CO.sub.2 hydrate 6 along the course of time is shown in FIG. 8.
FIG. 8 (A) shows changes in constituents of CH.sub.4 hydrate layer
2, and T-line, U-line, and E-line in FIG. 8(B) show changes in
temperature of the hydrate layer, changes in the rate of ultrasonic
waves, and changes in permeability of emulsion 5, respectively. As
shown in FIG. 8 (A), the layer 2 at the initial stage of
substitution comprises, for instance, sand and silt layer 17 and
voids 3, and CH.sub.4 hydrate 1 and seawater 24 exist in the voids
3.
[0090] When the emulsion 5 is injected into the voids 3 and thus
the liquid CO.sub.2 4 is supplied, CO.sub.2 hydrate 6 starts to
grow, and the temperature of the layer, i.e., the temperature of
solid phase and liquid phase begins to rise along with the hydrate
production, and thereby, the CH.sub.4 hydrate 1 starts to
decompose. CH.sub.4 gas 27 generated by the decomposition of the
CH.sub.4 hydrate 1 forms bubbles, and a part of the CH.sub.4 gas 27
is dissolved in seawater which flows the voids 3, namely,
groundwater 24. The bubbles of the CH.sub.4 gas 27 and the CH.sub.4
gas 27 dissolved in the groundwater 24 are collected along with the
groundwater 24 by the production well 8.
[0091] As shown in FIG. 8 (B), the temperature of the layer rises
due to the production of the CO.sub.2 hydrate. When the temperature
rising reaches a certain level, however, the decomposition of the
CH.sub.4 hydrate which is an endothermic reaction starts. Thus, it
is considered that the temperature at the end of the substitution
goes back to the level at the initial stage of the substitution,
because the endothermic heat due to the decomposition of the
CH.sub.4 hydrate and the exothermic heat due to the production of
the CH.sub.2 hydrate balance each other out, and the temperature
variation goes to be small. Therefore, the temperature of the layer
reflects the start and end of the hydrate production as well as the
start and end of the decomposition.
[0092] It is considered that the permeability of the emulsion 5 is
increased or decreased in proportion to the width of the portions
other than the CH.sub.4 hydrate 1 and the CO.sub.2 hydrate 6 in the
voids 3. When the bubbles of the generated CH.sub.4 gas become
larger and they are trapped in the voids 3, however, the permeation
of the emulsion comes to be impeded. Thus, it is considered that
the permeability of the emulsion 5 will be lowered by this impeded
extent. Thus, it is considered that, when the CH.sub.4 hydrate 1
starts to decompose, the permeability tends to decrease, and when
the CH.sub.4 hydrate 1 disappears as a result of completing it's
decomposition, the permeability tends to get better. Therefore, the
permeability of the emulsion 5 reflects the status of the hydrate
production as well as the status of the hydrate decomposition.
[0093] The ultrasonic waves tends to be reflected strongly at the
interface between the solid and gas when the acoustic impedance
becomes larger. On the other hand, in the sand and silt layer 17,
it is considered that the reflection, penetration, and refraction
of the ultrasonic waves would occur complicatedly. Since the speed
of the ultrasonic waves propagated through the solid is faster than
that through the liquid, the speed of the ultrasonic waves is
varied according to the condition of the voids 3. Further, the more
the solids of CH.sub.4 hydrate and CO.sub.2 hydrate exist in the
voids 3, the faster the speed of the ultrasonic waves becomes,
while the more the gas exists in the voids 3, the more likely the
ultrasonic waves are reflected. Therefore, as the production of
CO.sub.2 hydrate 6 starts, the speed of the ultrasonic waves
increases gradually. As the decomposition of CH.sub.4 hydrate 1
starts, however, the speed of the ultrasonic waves decreases
gradually. Further, when the CH.sub.4 hydrate 1 disappears as a
result of completing it's decomposition, and thus the volume of the
CH.sub.4 gas 27 decreases, the speed of the ultrasonic waves again
increases gradually. Therefore, the speed of the ultrasonic waves
reflects the status of the hydrate production as well as the status
of the hydrate decomposition.
[0094] As mentioned above, since the temperature of the layer 2,
the speed of the ultrasonic waves propagated through the layer 2,
and the permeability of the emulsion 5 into the voids reflects the
condition of the void 3, it is possible to presume the status of
substitution of CO.sub.2 hydrate 6 for CH.sub.4 hydrate 1 in the
voids 3 by monitoring such parameters.
[0095] The measurement of the temperature of the layer 2 can be
performed, for instance, by using a temperature sensor 18 which is
placed at the layer 2 where the CH.sub.4 hydrate has been produced.
The measurement of the ultrasonic waves can be performed, for
instance, by using an ultrasonic generator and an ultrasonic
receiver which are placed at the layer 2 where the CH.sub.4 hydrate
has been produced. In this embodiment, an ultrasonic generating and
receiving device 16 where the ultrasonic generator is integral with
an ultrasonic receiver is used. Namely, the ultrasonic generating
and receiving device 16 which is used for activating the CO.sub.2
molecules and for repressing the production of the CO.sub.2 hydrate
6 is also used for the measurement. The speed of the ultrasonic
waves propagated through the voids 3 can be determined by
receiving, at the receiving part of the ultrasonic generating and
receiving device 16, the ultrasonic waves for monitoring which has
been generated from the generation part of the device 16. Further,
the measurement of the permeability of the emulsion 5 into the
voids 3 can be performed, for instance, by a pressure gauge 15
which is provided on the liquid CO.sub.2 supplying line of the
injection well 7. By measuring the changes in the pressure of the
liquid CO.sub.2 4 passing through the injection well 7, the
permeability of the emulsion 5 can be determined.
[0096] Two or more of the temperature sensors 18 and two or more of
the ultrasonic generating and receiving devices 16 are placed along
a measuring line 28. The temperature sensors 18 and the ultrasonic
generating and receiving devices 16 are connected with cables 19,
and they are hanged from the communication control devices 20 which
are placed at the sea bottom into holes 21. In the layer 2 wherein
the CH.sub.4 hydrate have been produced, the temperature sensors 18
and the ultrasonic generating and receiving devices 16 are
alternately arranged, and in a seal layer 22 located on the layer
2, the temperature sensors 18 are provided. The individual
communication control devices 20 are connected to a computer which
is placed on the sea via communication and power cables 30.
Incidentally, in FIG. 3, the illustration for the temperature
sensors 18 and the ultrasonic generating and receiving devices 16
is omitted.
[0097] In the case of mining the gas hydrate, it is preferable to
form, on the gas hydrate layer as the target for mining, a seal
layer of a gas hydrate which is stable even at a high temperature
and a low pressure as compared with the gas hydrate to be mined, in
advance of the mining. For instance, in the case of mining CH.sub.4
hydrate in this embodiment, the substitution of hydrate is done
after the seal layer 22 of the CO.sub.2 hydrate is formed onto the
layer 2 where the CH.sub.4 hydrate has been produced. Since
CO.sub.2 can present stably in the form of hydrate even at a higher
temperature and lower pressure condition as compared with CH.sub.4,
CO.sub.2 is preferable as the seal layer 22 to be formed onto the
layer 2 where the CH.sub.4 hydrate has been produced. First, by
providing a injection well 29 which penetrates into a layer which
is located on the layer 2 where the CH.sub.4 hydrate has been
produced and of which temperature and pressure condition allows
CO.sub.2 to form its hydrate, and injecting the CO.sub.2-- water
emulsion 5 through the infusing well 29 into the voids 3 between
the solid particles in the layer, wherein the CO.sub.2-- water
emulsion 5 is being under condition that the liquid CO.sub.2 is
dispersed in the seawater in the form of minute particles smaller
than the voids 3, the seal layer 22 is formed. Thereafter, by
injected the above mentioned CO.sub.2-- water emulsion 5 into the
voids 3 between the solid particles in the layer 2 where the
CH.sub.4 hydrate has been produced, the CO.sub.2 hydrate is
produced therein, while the CH.sub.4 hydrate existed in the voids 3
is decomposed by utilizing the heat of reaction for the CO.sub.2
hydrate production. The CH.sub.4 gas 27 produced by the
decomposition of the CH.sub.4 hydrate is entrapped by the seal
layer 22 so as to be able to be collected through the production
well 8 without leaking out to the sea or the atmosphere. Thus, the
CH.sub.4 hydrate embedded in the layer can be recovered as CH.sub.4
gas while it is replaced with the CO.sub.2 hydrate.
[0098] Incidentally, in the case that the seal layer 22 is formed
by the production of gas hydrate but it is formed at a layer where
a natural gas hydrate is not embedded, depending on the
circumstance, it may be necessary to regulate temperature so as to
attain the temperature capable of producing the gas hydrate which
forms the seal layer 22, for instance, by regulating the
temperature of the emulsion 5 or regulating the mean diameter of
the minute particles of the liquid guest molecules, because the
endothermic heat due to the decomposition of the gas hydrate can
not be expected. For example, in the case that the guest molecules
are CO.sub.2, depending on the circumstance, it may be necessary to
take such a contrivance that the volume of the seawater to be mixed
with the minute particles 23 of the liquid CO.sub.2 in the
CO.sub.2-- water emulsion is increased, or that the temperature of
the seawater to be mixed is set to lower temperature. Separately,
it is also possible to repress the heating value per unit volume of
the emulsion 5 by varying the mixing ratio of the liquid CO.sub.2
and water in the emulsion. Further, it is also possible to regulate
the production rate of the CO.sub.2 hydrate by varying the particle
size of the minute particles of the liquid CO.sub.2 in the emulsion
5. Furthermore, it is also possible to activate the CO.sub.2
molecules by irradiating the emulsion 5 with the ultrasonic waves.
Alternatively, it is also possible to repress the production of the
hydrate during the irradiation by irradiating the emulsion 5 with
the ultrasonic waves.
[0099] Next, an embodiment of another method for mining of the gas
hydrate is shown in FIG. 11. In this method for mining the gas
hydrate, first, a dome-shaped seal layer 22 of the CO.sub.2 hydrate
is formed on a CH.sub.4 hydrate layer 32 as the target to be mined,
and a CO.sub.2 hydrate layer 33 which aims to fixate the CO.sub.2
hydrate is formed at a layer which is rested under the CH.sub.4
hydrate layer 32, and then, the temperature of this layer 33 into
which the CO.sub.2 emulsion is injected is risen by heat of
reaction in the CO.sub.2 hydrate production, and, the CH.sub.4
hydrate existing in the CH.sub.4 hydrate layer 32 which is rested
on this layer 33 is decomposed into water and CH.sub.4 gas from the
lower side by the risen temperature. The CH.sub.4 gas 27 generated
by the decomposition of the CH.sub.4 hydrate layer 32 is collected
by the dome-shaped seal layer 22 temporarily, and then it is
recovered through the production well 8 to the ground. In addition,
into the layer after mining the CH.sub.4 hydrate, the CO.sub.2--
water emulsion is injected by an operation of moving the injection
well 7 upward or an constitution of providing an another injection
well which penetrates into the CH.sub.4 hydrate layer 32, in order
to produce the CO.sub.2 hydrate therein. Thereby, solid phases such
as sand particles, which have been brought into a mutually
unconsolidated condition, can be consolidated by the CO.sub.2
hydrate, and thus the strength of the layer can be restored.
Therefore, it is possible to fixate a large amount of CO.sub.2 in
the form of stable hydrate as the three layers 22, 32, and 33 into
the submarine layer. Incidentally, since the region over the
CH.sub.4 hydrate layer 32 is stabilized by producing the CO.sub.2
hydrate which forms the seal layer 22 and by which the solid phases
in this layer are consolidated in advance of mining the CH.sub.4
hydrate, even if a submarine landslide on a large scale will happen
due to an earthquake or the like, there is not very much risks
about the leak of the CH.sub.4 gas obtained by the decomposition of
the CH.sub.4 hydrate into the atmosphere, and about the release of
the CH.sub.4 hydrate which has a lower density than the seawater
into the atmosphere as a result of ascending the CH.sub.4 hydrate
with the buoyancy and then allowing it to gasify.
[0100] Although the above mentioned embodiments are preferable
embodiments of the present invention, many and various changes or
modifications can be made unless they are deviated from the spirit
and range of the present invention. Although the present invention
is described by exemplifying the fixation of CO.sub.2 by hydration,
the substitution of CO.sub.2 hydrate with CH.sub.4 hydrate, and the
mining of CH.sub.4 hydrate in the above mentioned embodiments, the
guest molecules to be targeted is not limited thereto. It would be
clearly understood that the present invention can be applied to all
guest molecules which can form a gas hydrate. With respect to the
substitution of the hydrate, it can be also applied to any
combinations of two guest molecules which are different from each
other regarding the temperature and pressure condition for stably
existing in their hydrate forms. For example, as the guest
molecules of natural gas hydrate, methane (CH.sub.4), ethane
(C.sub.2H.sub.6), propane (CH.sub.3CH.sub.2CH.sub.3), carbon
dioxide (CO.sub.2), hydrogen sulfide (H.sub.2S), air (nitrogen
N.sub.2) are known, and it will be clearly understood that the
methods according to the present invention can be applied to the
production, substitution, and mining of the gas hydrate of these
guest molecules.
[0101] Further, although in the abovementioned embodiment the
methods for production, substitution, and mining of the gas hydrate
in the submarine layer which mainly comprises the sand layer are
described, as a matter of course, the present invention can be
applied to the layer such as CH.sub.4 hydrate layer below a lake
bottom, CH.sub.4 hydrate layer of a permafrost, etc. Further, since
in the present invention the guest molecules are injected, in the
form of emulsion 5 which includes water necessitated for the
production of hydrate, into the voids of the layer, it is possible
to perform the fixation, the substitution, and the mining owing to
the production of the hydrate of the guest molecules, aimed at a
layer where water does not exist in the voids thereof.
[0102] In addition, depending on the status of the layer, in order
to adjust the ratio of the liquid CO.sub.2 and water in the
emulsion 5, the liquid CO.sub.2, water/seawater 24, may be allowed
to flow through the outer pipe 10, and the inner pipe 11,
respectively, and the water/seawater 24 may be allowed to be
sprayed into the liquid CO.sub.2. Further, although in the
abovementioned embodiments the emulsion is prepared by injecting
the liquid CO.sub.2 into the water/seawater in advance of injecting
the emulsion into the layer, depending on the circumstances, it is
also possible to inject the liquid CO.sub.2 directly from a splay
nozzle into the layer where the CH.sub.4 hydrate exists so as to
disperse the liquid CO.sub.2 as minute particles into the seawater
or the like in the layer and to form the emulsion, and thereafter,
to diffuse the emulsion into the layer by utilizing of the energy
given by the injection.
EXAMPLES
Example 1
[0103] Room experimentation was performed in order to confirm
whether the diameters of minute particles of the liquid CO.sub.2
which are suspended in the CO.sub.2-- water emulsion can be made to
be smaller than the size of voids in a sedimentary layer (voids
between solid phases). This experimentation was conducted with
respect to a sand layer in the Nankai trough which is a promising
target for mining of the CH.sub.4 hydrate. This sand layer in the
Nankai trough includes clay (particle size: 0.005-0.001 mm) and
silt (particle size: 0.075-0.005 mm) at about 20%. The percentages
of penetrated weight thereof were shown in FIG. 12. Although the
sample of the sand layer in the Nankai trough had been obtained by
trial diggings presided by Ministry of Economy, Trade and Industry
of Japan, it is difficult for me, the inventor, to obtain the
sample. Therefore, the experimentation was conducted by using
Toyoura sand in the range of 0.1-0.6 mm which was adjusted to the
percentage of penetrated weight shown in FIG. 12 as an indicator
for the room experimentation. The atomization of the liquid
CO.sub.2 was proceeded by using a spray nozzle manufactured by H.
Ikeuchi & Co., Ltd. (Product Code: 1/4MKB 80 063N S303-RW)
according to the spray method. When spraying water from this nozzle
under normal temperature and normal pressure and by setting the
inner pressure to 1 MPa, the diameter of water drops were in the
range of 30-40 .mu.m. However, the spraying condition for the
liquid CO.sub.2 was unknown. Thus, assuming that the condition for
the liquid CO.sub.2 would adhere to that for the water, the
differential pressure between a pressure vessel 34 into which the
liquid CO.sub.2 was charged and an atomizing pressure vessel 35 on
which the nozzle was provided was set to 1 MPa, with respect to the
spraying pressure.
[0104] The experimentation was conducted by using the experimental
instrument as shown in the schematic diagram of FIG. 13. Three
pressure vessels, i.e., the liquid CO.sub.2 pressure vessel 34, the
liquid CO.sub.2 atomizing pressure vessel 35, and a microscopic
observing pressure vessel 37, which were mutually connected by pipe
lines, constituted the experimental instrument. Into the liquid
CO.sub.2 pressure vessel 34, CO.sub.2 was injected at the room
temperature, so that the CO.sub.2 gas was charged over the liquid
CO.sub.2 layer. Into the liquid CO.sub.2 atomizing pressure vessel
35, water was injected, and then the CO.sub.2 gas was charged over
the water. Incidentally, in this figure, the numerals 45, 46, 51,
52, 53, 54 denote a water tank, hot-water, a pump, a valve, and a
tank for liquid CO.sub.2, and a thermometer, respectively.
[0105] Into the liquid CO.sub.2 pressure vessel 34, carbon dioxide
which had been liquidized under an initial condition that the
temperature was 19.degree. C. (room temperature) and the pressure
was 5.2 MPa was sealed, and then it was warmed in hot water. When
the temperature and the pressure reached 25.degree. C. and 6.2 MPa,
respectively, the valve 44 was opened to supply the liquid CO.sub.2
to the atomizing pressure vessel 35. In the atomizing pressure
vessel 35, the liquid CO.sub.2 was sprayed through the spray nozzle
(not shown in the figure) toward the CO.sub.2 gas as an upper layer
in the atomizing pressure vessel 35, and then the minute particles
of the liquid CO.sub.2 thus formed fell into the water layer as an
lower layer in the pressure vessel 35 which was stirring with a
stirrer, thus the CO.sub.2-- water emulsion was prepared.
Incidentally, before the warming in hot water, the inner pressure
in the liquid CO.sub.2 pressure vessel 34 and the inner pressure in
the atomizing pressure vessel 35 were equalized by opening the
valve 43.
[0106] Thereafter, the CO.sub.2-- water emulsion thus prepared were
introduced into the microscopic observing pressure vessel 37 by
opening the valve 47, and the microscopic observation was done. The
CO.sub.2-- water emulsion in the sampling room which was formed
between pressure-proof glasses of 10 mm in thickness of the
microscopic observing pressure vessel 37 was observed by using a
stereo-microscope of 60 times magnification (manufactured by Nikkyo
Technos, Co., Ltd., under the product code: S-20L(60 X)). After the
observation, by using the microscopic photograph (See, FIG. 14),
the diameters and counts of minute particles at the three points
(a, b, c) were examined. The relations between the diameter and
count of liquid CO.sub.2 at the three points were as shown in Table
1. When the relation between the particle sizes of the liquid
CO.sub.2 and the percentages of penetrated weight was determined,
it was found that the diameters of the liquid CO.sub.2 were within
the range of 10-100 .mu.m as shown in FIG. 16, and thus they were
sufficiently smaller than the Toyoura sand (100-600 .mu.m) (See,
FIG. 15). In addition, it was similar in distribution to the
Toyoura sand.
TABLE-US-00001 TABLE 1 D (mm) (a) (b) (c) Total 0.100 .ltoreq. D 1
3 2 6 0.084 .ltoreq. D < 0.100 3 6 1 10 0.062 .ltoreq. D <
0.084 3 9 7 19 0.047 .ltoreq. D < 0.062 9 6 8 23 0.034 .ltoreq.
D < 0.047 16 16 10 42 0.026 .ltoreq. D < 0.034 14 15 5 34
0.018 .ltoreq. D < 0.026 25 19 12 56 0.010 .ltoreq. D < 0.018
47 23 35 105 Total 118 97 80 295
[0107] Judging from these results, the emulsion which includes a
large volume of liquid CO.sub.2 can enter into the voids between
the solid phases such as sand particles while it puts the seawater
or water filled in the voids away from the void, that is, the
CO.sub.2 particles which are smaller than the voids in the layer
where the gas hydrate have been produced, i.e., the voids between
the solid phases (sand particles) can flow through the voids, as is
the case with water.
Example 2
[0108] The behavior for the production of CO.sub.2 hydrate when the
CO.sub.2 water emulsion obtained in Example 1 was permeated into
the Toyoura sand in the CO.sub.2 hydrate producing pressure vessel
42 which simulated the sand layer in the ocean sedimentary layer
was observed by using as indicators the temperature and pressure.
The schematic diagram of the experimental instrument used in the
production of the CO.sub.2 hydrate is shown in FIG. 13. This
experimental instrument was the same as in Example 1 except that
the CO.sub.2 hydrate producing pressure vessel 36 was further
connected downstream from the liquid CO.sub.2 atomizing pressure
vessel 35. The inside of the CO.sub.2 hydrate producing pressure
vessel 36 were pressurized by a hand-operated pump 39 under the
condition that the water was supplied into the CO.sub.2 hydrate
producing pressure vessel 36 from a not-shown water tank. The
CO.sub.2 hydrate producing pressure vessel 36 were charged with the
Toyoura sand and water which simulated the sand layer in the ocean
sedimentary layer, the sand layer being within the range of the
particle diameters shown in FIG. 12, so as to satisfy a porosity of
about 50%. Incidentally, in this experiment, since there is no
necessary to confirm the condition of the CO.sub.2-- water
emulsion, the CO.sub.2 hydrate producing pressure vessel 36 may be
connected directly to the liquid CO.sub.2 atomizing pressure vessel
35 in the downstream of the pressure vessel 35. The numeral 45
represents a pressure gauge.
[0109] First, to, the CO.sub.2 hydrate producing pressure vessel 36
which had been charged with 314.09 g of the Toyoura sand saturated
with 79.47 g of water and which had been pressurized up to about 5
MPa by using the hand-operated pump 39, 30.78 g of the CO.sub.2--
water emulsion were introduced from the upside of the pressure
vessel 36, under the condition that a valve which was located at
the downside of the pressure vessel 36 was slightly opened to an
extent that the pressure inside the pressure vessel 36 was not
decreased, so that the water existing in the voids were extruded
from the pressure vessel 36 by the emulsion and the emulsion was
introduced into the pressure vessel. Upon when the emulsion was
discharged from the downside of the pressure vessel, the valve was
closed. At this condition, the water contained in the pressure
vessel was 48.69 g. Then, by utilizing the iced water 50 in the
water tank 38, the pressure vessel was cooled down for two hours to
a temperature that is a stable condition for the CO.sub.2 hydrate,
in order to produce the CO.sub.2 hydrate. Incidentally, the
injection of the liquid CO.sub.2-water emulsion was proceeded by
opening the valve 48 so as to introduce the liquid CO.sub.2-- water
emulsion which had been prepared in the liquid CO.sub.2 atomizing
pressure vessel 35 into the CO.sub.2 hydrate producing pressure
vessel 36. The discharge of the emulsion can be easily detected
because the fact that the pressure falls to the atmospheric
pressure allows the minute particles of the liquid CO.sub.2 in the
emulsion to vaporize.
[0110] The temperature changes in the pressure vessel 36 at that
time which were measured by thermometers 42 located at the six
points shown in FIG. 17 is shown in FIG. 18. According to the
results of the measurements, the temperatures at the six points
rose at the same time and in similar fashion. It is considered that
these temperature changes were due to a phenomenon that CO.sub.2
hydrate was produced uniformly, and it is also considered that
CO.sub.2 was dispersed uniformly throughout the sample. By the way,
the inner pressure of the vessel was varied within the range of 4-9
MPa.
[0111] In this experiment, the pressure vessel 36 was dipped in the
iced water, and thus, this experiment was performed under the
boundary condition that the heat could be dissipated (heat
transmission). The values of temperature rising at the respective
measurement points T3-T8 were about 4.degree. C. However, in the
case of the actual ocean sedimentary layer, there are boundaries
where the initial temperature is not changed. Thus, under the
boundary condition that the initial temperature is not changed, a
non-steady thermal diffusion analysis was conducted. As the result,
it was found that the temperature of the sample (mixture of the
Toyoura sand, water and CO.sub.2) used as an indicator was risen at
about 9.degree. C. by the heat of reaction for the CO.sub.2 hydrate
production. Since the theoretically calculated maximum temperature
rising of the Toyoura layer (mixture of sand, water and CO.sub.2)
by the heat of the reaction (absolute value) for the CO.sub.2
hydrate production is about 9.degree. C., the experimental result
meant that the environment near the condition that the maximum
temperature rising can be produced was held. Namely, the result
makes it clear that, by the atomization of and the emulsifying of
the liquid CO.sub.2, the ideal hydrate producing reaction is
caused, in other words, the production rate of the CO.sub.2 hydrate
can be accelerated, and still further, the liquid CO.sub.2-- water
emulsion can be dispersed uniformly into the sand layer. In
addition the result makes it clear that the CO.sub.2 can be
utilized as a heating agent for the layer where the CH.sub.4
hydrate exists.
[0112] From the results of Examples 1 and 2, it can be judged that
the CO.sub.2 particles which are smaller than the voids flowed in
the voids in the layer or the Toyoura sand layer, as is the case
with water.
<Control 1>
[0113] Into the pressure vessel 36 which had been charged with
314.09 g of the Toyoura sand saturated with 79.47 g of water and
which had been pressurized up to about 5 MPa by using the
hand-operated pump 39, 27.14 g of liquid CO.sub.2 of which pressure
had been risen to about 1 MPa by dipping into hot water were
introduced, and at the same time, about 25 cc of water were drawn
out from the downside of the pressure vessel 36 by using the
hand-operated pump. Upon when the liquid CO.sub.2 was discharged
from the downside of the pressure vessel, the valve was closed. The
discharge of the liquid CO.sub.2 can be easily detected because the
fact that the pressure falls to the atmospheric pressure allows the
liquid CO.sub.2 to vaporize. At this condition, the water contained
in the pressure vessel was 50.85 g. Then, by utilizing the iced
water 50 in the water tank 38, the pressure vessel was cooled down
for two hours to a temperature that is a stable condition for the
CO.sub.2 hydrate, in order to produce the CO.sub.2 hydrate.
[0114] The actual measurement data of the temperature changes at
the six points in the Toyoura in case is shown in FIG. 17.
According to the results of the measurements, the temperature
changes at the six points were caused randomly with time
differences. Further, with respect to the value of the temperature
rising, the values of the individual points were mutually distinct,
and the values, even the maximum, did not reach 2.degree. C.
Further, at the measuring point of being the minimum temperature
change, the temperature rising was hardly observed. From these
results, it is considered that the liquid CO.sub.2 was not
dispersed uniformly into the voids in the Toyoura sand layer, and a
large variation was caused in the dispersion, and further,
depending on places, the liquid CO.sub.2 was not supplied. Further,
since there was a variation in the values of the temperature rising
at the respect measuring points, and the values of the temperature
rising, per se, were low, it was shown that the reaction rate for
the hydrate production was slow and the reaction were not
progressed actively.
* * * * *