JP2005290334A - Hydrate treatment apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easily operable hydrate treating apparatus with a simple and down sized construction, low cost production, low running cost and an improved hydrate treatment efficacy. <P>SOLUTION: The apparatus puts in a transfer and mixing vehicle capable of transfer with mixing in axial direction, equipped with a hydrate supplying inlet and a gas supply inlet containing hydrate forming substance at the front and an outlet at the back to exhaust the hydrate, surrounded with a space for a cooling medium outside of the main body of apparatus to supply the cooling medium in the space. The transfer and mixing vehicle is made of paddle or ribbon type connecting to a screw press type dehydrating apparatus at the front of the apparatus so as to drive a rotary shaft with a common driving part. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrate treatment apparatus for treating hydrate produced by reacting water and a gas containing a hydrate-forming substance.

  Currently, natural gas mainly composed of hydrocarbons such as methane has been used effectively, but natural gas collected from gas fields is cooled to the liquefaction temperature by storing and transporting natural gas for that purpose. A method of storing and transporting as liquefied natural gas (LNG) is employed.

  However, for example, in the case of methane, which is the main component of liquefied natural gas, an extremely low temperature of −162 ° C. is required for liquefaction, so a dedicated storage facility and a dedicated LNG transport ship are required, and the cost of storage and transport is high. Therefore, it is the fact that it is not so much adopted except in the large gas field.

  Therefore, in recent years, especially in small and medium-sized gas fields, natural gas is hydrated to produce a solid state hydrate (hydrate), and the hydrate is stored and transported in the solid state. Has been studied (for example, Patent Document 1).

  FIG. 7 is a process diagram showing an example of a conventional hydrate manufacturing process described in Patent Document 1 described above.

  In the figure, S1 is a production process in which water and natural gas are reacted at a temperature higher than the freezing point (about 0 ° C. to 5 ° C.) and higher than atmospheric pressure (about 4 MPa or more) to generate a hydrate. A production reactor of the formula is used.

  S2 is a physical dehydration step in which water is physically dehydrated from the hydrate and water slurry produced in the production step S1, and for example, a screw press type dehydrator is used.

  S3 is a hydration dehydration step in which the residual water contained in the hydrate after the physical dehydration in the physical dehydration step S2 is dehydrated by reacting with natural gas at a lower temperature (about −5 ° C. to 0 ° C.) than in the production step S1. For example, a twin-screw type dehydrator is used.

  S4 is a cooling step for cooling the hydrate dehydrated and dehydrated in the hydration dehydration step S3 to a temperature below the freezing point (about −25 ° C. to −20 ° C.) that does not decompose even under low pressure. in use.

  S5 is a depressurizing step for depressurizing the hydrate cooled in the cooling step S4 to the atmospheric pressure, and for example, a valve switching depressurizing device is used.

  S6 is a molding process for molding the hydrate decompressed in the decompression process S5. For example, a pressure press mold molding apparatus is used.

  The hydrate formed and solidified in the forming step S6 is stored in a transport container (not shown) and stored frozen, or transported and stored together with the transport container, and the stored hydrate is stored as needed. The gas is then gasified by the cracking device and sent to the consumer.

  FIG. 8 is an explanatory diagram showing the configuration of the generation step S1, the physical dehydration step S2, the hydration dehydration step S3, and the cooling step S4 shown in FIG.

  In the figure, reference numeral 1 denotes a cylindrical vertical generation container for generating a hydrate by a generation reaction. The generation container 1 is supplied with water from a water storage tank (not shown) via a water pipe 2, and a liquid phase L is introduced into the generation container 1. The liquid phase L is configured to maintain a predetermined water level by controlling a water supply pump and a valve (not shown) provided in the water pipe 2.

  The production vessel 1 is supplied with low-temperature and high-pressure natural gas stored in a gas storage unit (not shown) via a gas pipe 3 to form a gas phase G in the production vessel 1, and is provided in the gas pipeline 3. Further, the opening degree of the flow rate control valve (not shown) is controlled so that the pressure of the gas phase G is maintained at about 4 MPa or more, which is the hydrate generation pressure.

  A water pipe 4 is connected to the bottom and top of the production vessel 1 as shown in the figure. The water pipe 4 has a filter and a valve (not shown), a water circulation pump 5, a heat exchanger 6, and a valve (not shown). Are sequentially provided, and a spray nozzle 7 is provided at the tip of the water pipe 4 protruding inward from the top of the production container 1.

  As a result, the water extracted from the bottom of the production container 1 is cooled to a necessary temperature by the heat exchanger 6 while being circulated by the water circulation pump 5, and is sprayed by the spray nozzle 7 to produce hydrate. .

  Further, on the side surface of the production vessel 1 close to the liquid level of the liquid phase L, a slurry outlet 8 for extracting the hydrate and water slurry floating on the liquid level is provided. The slurry outlet 8 is connected to the slurry pipe 9. Via a screw press type dehydrator 10.

  The slurry pipe 9 is provided with a slurry extraction pump 11 together with a valve (not shown), and the slurry hydrate and water that float on the liquid surface of the liquid phase L in the generation vessel 1 are removed from the slurry outlet 8. And is supplied to the screw press type dehydrator 10.

  The screw press type dehydrating apparatus 10 is a shaft body having a cylindrical screen (mesh) -shaped filter medium 12 inside a main body having a cylindrical inner space and a spiral protrusion on a side surface and disposed in the inner space. The screw rotation shaft 13 and the drive unit 14 that drives the screw rotation shaft 13 are configured. The hydrate and water slurry extracted by the slurry extraction pump 11 are screwed through the slurry pipe 9. The hydrate supplied and physically dehydrated to the upstream end of the press type dehydrator 10 is discharged from the rear end of the screw press type dehydrator 10 on the downstream side through the hydrate discharge pipe 15. Then, it will be supplied to the subsequent hydration dehydration step S3.

  The water physically dehydrated by the screw press type dehydrator 10 is extracted from the bottom of the main body on the tip side of the screw press type dehydrator 10 and returned to the forming container 1 through the water pipe 16. It has become.

  Next, the hydrate after physical dehydration discharged from the rear end portion of the screw press type dehydrator 10 through the hydrate discharge pipe 15 is supplied to the front end portion of the subsequent twin-screw type dehydrator 17. .

  The biaxial screw-type dewatering device 17 includes a screw rotation shaft 18 that is a shaft body having a spiral protrusion on a side surface and disposed in the internal space inside a main body having an elliptical cylindrical internal space. The two are arranged so that the spiral protrusions overlap each other and are each driven by the drive unit 19. A gas pipe 20 is provided at the rear end of the biaxial screw type dehydrator 17. Natural gas is supplied to the interior space, and the interior space is controlled to a temperature suitable for the hydration reaction by a cooling means (not shown).

  Since the twin-screw dehydrator 17 is configured as described above, the hydrate supplied to the twin-screw dehydrator 17 from the tip via the hydrate discharge pipe 15 is driven by the screw rotating shaft 18. -5 ° C. to 0 ° C., which is a temperature suitable for the hydration reaction while being stirred and in contact with the natural gas supplied from the rear end through the gas pipe 20 while being conveyed in the axial direction toward the rear end By being cooled to about 0 ° C., it reacts with moisture remaining in the hydrate to be dehydrated and dehydrated, and the hydrate after dehydration and dehydration is from the rear end portion on the downstream side of the twin-screw dehydrator 17. It is discharged through the hydrate discharge pipe 21 and supplied to the subsequent cooling step S4.

  Next, the hydrate after dehydration discharged from the rear end portion of the twin screw type dehydrator 17 through the hydrate discharge pipe 21 is supplied to the front end portion of the screw conveyor type cooling device 22 at the subsequent stage. Yes.

  The screw conveyor type cooling device 22 includes a screw rotating shaft 23 which is a shaft body having a spiral protrusion on a side surface and disposed in the inner space inside a main body having a cylindrical inner space, and a screw rotating shaft 23. It is comprised from the drive part 24 which drives.

  The hydrate dehydrated and dehydrated by the biaxial screw type dehydrator 17 is hydrated in the internal space while being conveyed in the axial direction toward the rear end by driving the screw rotating shaft 23 in the screw conveyor type cooling device 22. Is cooled to about −25 ° C. to −20 ° C., which is a low temperature below the freezing point that does not decompose even under low pressure.

  The hydrate cooled to an appropriate temperature by the screw conveyor type cooling device 22 is discharged from the rear end portion on the downstream side of the screw conveyor type cooling device 22 through the hydrate discharge pipe 25 and is not shown. The pressure is supplied to the decompression step S5.

  The main body of the screw conveyor type cooling device 22 is composed of a double cylinder from an outer cylinder and an inner cylinder, and a refrigerant space 26 formed between the outer cylinder and the inner cylinder is connected via a refrigerant pipe 27. Cooling means is employed in which a cooling refrigerant is circulated and the inside of the main body having a cylindrical inner space is controlled to an appropriate cooling temperature.

The refrigerant pipe 27 is provided with an accumulator, an expansion valve, etc. (not shown) together with a refrigerant circulation pump 28 and a heat exchanger 29 to constitute a refrigerant circulation circuit. As the refrigerant, CO ₂ , NH ₃ , R ₁₂ etc. are used.

  The hydrate treated as described above is depressurized to atmospheric pressure in a subsequent decompression step S5 (not shown), and then molded and solidified in a molding step S6, and then stored in a transport container (not shown). The hydrate is stored in a frozen state or transported to a destination together with a transport container, and the stored hydrate is gasified by a cracking device as needed and sent to a consumer.

  However, in the conventional hydrate treatment apparatus configured as described above, in order to process the hydrate produced in the production vessel 1, in the physical dehydration step S2, for example, the screw press type dehydrator 10, water In the sum dewatering step S3, for example, a twin screw type dewatering device 17 and in the cooling step S4, for example, a screw conveyor type cooling device 22, an independent processing device is provided for each step, and these are connected to the hydrate discharge pipe 15 , 21 and the like to supply hydrate, the apparatus configuration is complicated, and it is difficult to make the processing apparatus compact. In addition, separate driving units 14 are used to drive the processing apparatuses. , 19 and 24 are required, and there is a problem that the processing apparatus becomes expensive.

In the hydration dehydration step S3, for example, in order to maintain the interior space of the twin screw dehydrator 17 at a temperature suitable for the hydration reaction, it must be cooled to about −5 ° C. to 0 ° C. In the cooling step S4, for example, in the internal space of the screw conveyor type cooling device 22, the hydrate must be cooled to about −25 ° C. to −20 ° C., which is a low temperature below the freezing point that does not decompose even under low pressure. Separate cooling means are required, the hydrate processing efficiency is not very good, and the running cost is high.
JP 2003-105362 A (FIGS. 1 and 2)

  The present invention has been made in view of the above-described conventional problems. The apparatus configuration of a hydrate treatment apparatus produced by reacting water and a gas containing a hydrate-forming substance is simplified, and can be made compact and inexpensive. To provide a practically extremely effective hydrate processing apparatus that can be manufactured at a low cost, can improve the processing efficiency of hydrate at a low running cost, is easy to handle, and can solve the conventional problems. Is an issue.

  The present invention has been made to solve the above-described conventional problems, and each of the inventions described in the claims includes the following means (1) to (15) as hydrate processing apparatuses. Adopted.

  (1) The first means accommodates a transfer mixing means for mixing while transferring in the axial direction, a hydrate supply port for supplying hydrate at the front end portion, and a hydrate for discharging hydrate at the rear end portion. A gas supply port for supplying a gas containing a hydrate-forming substance is provided at the tip of the container body having a rate discharge port, a refrigerant space is provided on the outer periphery of the container body, and a cooling refrigerant is provided in the refrigerant space. It is characterized in that it is made to supply.

  (2) The second means is characterized in that, in the hydrate treatment apparatus adopting the first means, the hydrate supply port and the gas supply port are common.

  (3) The third means is characterized in that, in the hydrate treatment apparatus adopting the first or second means, the transfer mixing means has a rotating shaft with paddles attached at intervals in the axial direction. It is.

  (4) The fourth means is characterized in that, in the hydrate treatment apparatus adopting the first or second means, the transfer and mixing means has a rotating shaft attached with a ribbon at an interval in the axial direction. It is.

  (5) The fifth means is a hydrate treatment apparatus adopting any one of the first to fourth means, wherein the hydrate supply port provided at the tip of the container body is provided at the tip surface of the container body. The hydrate discharge opening provided on the rear end face of the physical dehydration apparatus that physically dehydrates the hydrate through the opening is characterized in that it is communicated with the opening.

  (6) The sixth means is characterized in that, in the hydrate treatment apparatus adopting the fifth means, the physical dehydrator is a screw press type dehydrator.

  (7) A seventh means is a hydrate treatment apparatus adopting the sixth means, wherein the screw rotating shaft of the screw press type dehydrating device and the rotating shaft of the transfer mixing means are connected and driven by a common drive unit. It is characterized by doing so.

  (8) The eighth means is characterized in that, in the hydrate treatment apparatus adopting the seventh means, there are a plurality of screw rotation shafts of the screw press type dewatering device and a plurality of rotation shafts of the transfer mixing means. .

  (9) A ninth means is characterized in that, in a hydrate treatment apparatus adopting any one of the first to fourth means, a heating facility is provided at the hydrate supply port.

  (10) A tenth means is a hydrate treatment apparatus adopting any one of the first to fourth means, wherein a scraping device is provided at the hydrate supply port.

  (11) The eleventh means is characterized in that in the hydrate processing apparatus adopting any one of the first to fourth means, the hydrate supply port is lined.

  (12) The twelfth means is characterized in that, in the hydrate processing apparatus adopting the third means, the length of the arm of the paddle near the hydrate supply port is made shorter than the length of the arm of the other paddle. To do.

  (13) A thirteenth means is characterized in that a paddle is lined in a hydrate processing apparatus employing the third means.

  (14) The fourteenth means is characterized in that, in the hydrate treatment apparatus adopting the fourth means, the length of the ribbon arm near the hydrate supply port is made shorter than the length of the other ribbon arm. To do.

  (15) A fifteenth means is characterized in that a ribbon is lined in a hydrate processing apparatus adopting the fourth means.

  Since the invention according to each claim described in the claims employs the means described in the above (1) to (15), it has the following effects.

  (1) Since the invention according to claim 1 employs the first means, the hydrate is hydrated and dehydrated by the gas containing the hydrate-forming substance supplied at the tip in the container body, and later It can be mixed while being transported in the axial direction toward the end, cooled to an appropriate temperature and discharged, and hydration dehydration and cooling can be performed by the refrigerant supplied to the refrigerant space provided on the outer periphery of the container body. Since it is made in the same container body, it is not necessary to install a hydration dehydration device and a cooling device separately and drive them with separate drive units, or to provide a cooling means for hydration dehydration and cooling separately. However, the processing apparatus can be manufactured at a low cost.

  (2) Since the invention according to claim 2 employs the second means, in addition to the effect of the invention according to claim 1, it is not necessary to provide the hydrate supply port and the gas supply port separately. The apparatus configuration is simpler and more compact, and the processing apparatus can be manufactured at a low cost.

  (3) Since the invention according to claim 3 employs the above-mentioned third means, in addition to the effect of the invention according to claim 1 or claim 2, the paddle type generally used as a transfer mixing means Therefore, it is easy to manufacture and handle and can be manufactured at a lower cost.

  (4) Since the invention according to claim 4 employs the fourth means, in addition to the effect of the invention according to claim 1 or 2, the ribbon type generally used as a transfer mixing means Therefore, it is easy to manufacture and handle and can be manufactured at a lower cost.

  (5) Since the invention according to claim 5 employs the fifth means, in addition to the effects of the invention according to any one of claims 1 to 4, hydrate physical dehydration and hydration dehydration Cooling can be performed continuously in direct communication, the apparatus configuration is further simplified and the apparatus can be made more compact, and the processing apparatus can be manufactured at low cost.

  (6) Since the invention according to claim 6 employs the sixth means, in addition to the effect of the invention according to claim 5, a screw press type dehydrator generally used as a physical dehydrator is provided. It can be used, can be manufactured and handled easily, and can be manufactured at a lower cost.

  (7) Since the invention according to claim 7 employs the seventh means, in addition to the effect of the invention according to claim 6, the screw rotation shaft of the screw press type dehydrator and the rotation shaft of the transfer mixing means are provided. It can drive with a common drive part, and can manufacture a processing apparatus further cheaply.

  (8) Since the invention according to claim 8 employs the eighth means, in addition to the effect of the invention according to claim 7, a large amount of hydrate can be efficiently processed.

  (9) Since the invention according to claim 9 employs the ninth means, in addition to the effects of the invention according to any one of claims 1 to 4, by the heating equipment provided at the hydrate supply port By heating, blockage of the hydrate in the vicinity of the hydrate supply port can be prevented, and a large amount of hydrate can be processed efficiently.

  (10) Since the invention according to claim 10 employs the tenth means, in addition to the effect of the invention according to any one of claims 1 to 4, a scraping device provided at the hydrate supply port By scraping, the hydrate blockage near the hydrate supply port can be prevented, and a large amount of hydrate can be processed efficiently.

  (11) Since the invention according to claim 11 employs the eleventh means, in addition to the effect of the invention according to any one of claims 1 to 4, by lining the hydrate supply port, It is difficult to adhere to the hydrate supply port to prevent clogging of the hydrate, and a large amount of hydrate can be processed efficiently.

  (12) Since the invention according to claim 12 employs the twelfth means, in addition to the effect of the invention according to claim 3, the length of the arm of the paddle near the hydrate supply port is set to the other paddle. By making it shorter than the length of the arm, hydrate can be smoothly supplied from the hydrate supply port into the container body to prevent the hydrate from being blocked, and a large amount of hydrate can be processed efficiently.

  (13) Since the invention according to claim 13 employs the thirteenth means, in addition to the effect of the invention according to claim 3, it is difficult to adhere to the paddle by lining the paddle, and the hydrate Occlusion is prevented and a large amount of hydrate can be processed efficiently.

  (14) Since the invention according to claim 14 employs the fourteenth means, in addition to the effect of the invention according to claim 4, the length of the arm of the ribbon near the hydrate supply port is set to the length of another ribbon. By making it shorter than the length of the arm, the hydrate can be smoothly supplied from the hydrate supply port into the container body to prevent the hydrate from being blocked, and a large amount of hydrate can be processed efficiently.

  (15) Since the invention according to claim 15 employs the fifteenth means, in addition to the effect of the invention according to claim 4, it is difficult to adhere to the ribbon by lining the ribbon, and the hydrate Occlusion is prevented and a large amount of hydrate can be processed efficiently.

  The best mode for carrying out the present invention will be described based on the following Examples 1 to 5.

  FIG. 1 is an explanatory diagram showing the configuration of the hydrate treatment apparatus according to Embodiment 1 of the present invention, which performs the processes of the hydration dehydration step S3 and the cooling step S4 shown in FIG.

  In the figure, reference numeral 30 denotes a cylindrical container main body, which is provided with a hydrate supply port 31 for supplying hydrate at the front end thereof, and for discharging the hydrate processed in the container main body 30 at the rear end thereof. A discharge port 32 is provided.

  Further, inside the container body 30 is housed a transfer mixing means 35 having a rotating shaft 34 with paddles 33 attached at intervals in the axial direction, and the rotating shaft 34 of the transferring and mixing means 35 is a drive unit 36. It is driven by.

  Further, a gas supply port 37 for supplying a gas such as a natural gas or a mixed gas containing a hydrate-forming substance such as methane or propane is provided at the tip of the container body 30.

  Further, the outer periphery of the container body 30 is configured as a double cylinder from an outer cylinder and an inner cylinder, and a cylindrical refrigerant space 38 formed between the outer cylinder and the inner cylinder is cooled via a refrigerant pipe 39. Cooling means is employed in which the refrigerant for the operation is supplied and the internal space of the container body 30 is controlled to an appropriate cooling temperature.

The refrigerant pipe 39 is provided with an unillustrated accumulator, an expansion valve, and the like together with the refrigerant circulation pump 40 and the heat exchanger 41 to constitute a refrigerant circulation circuit. As the refrigerant, CO ₂ , NH ₃ , R ₁₂ etc. are used.

  Since the hydrate processing apparatus of the present embodiment is configured as described above, the hydrate supplied from the hydrate supply port 31 to the tip of the container body 30 rotates the rotating shaft 34 by the drive unit 36. The paddle 33 is mixed while being transported in the axial direction inside the container body 30, and the processed hydrate is discharged from the hydrate discharge port 32 at the rear end of the container body 30.

  At this time, the hydrate supplied from the hydrate supply port 31 to the tip of the container body 30 is physically dehydrated in the preceding physical dehydration step S2, but is included in the physically dehydrated hydrate. Residual water is mixed by the paddle 33 while the hydrate is transported in the axial direction inside the container main body 30, so that the gas containing the hydrate-forming substance supplied from the gas supply port 37 at the distal end of the container main body 30. And is cooled to about −5 ° C. to 0 ° C., which is a temperature suitable for the hydration reaction while being stirred, so that it reacts with moisture remaining in the hydrate and is immediately hydrated and dehydrated.

  The hydrate dehydrated and dehydrated at the tip of the container body 30 is supplied to the refrigerant space 38 by being mixed by the paddle 33 while the hydrate is transported in the axial direction inside the container body 30. Due to the heat of vaporization of the refrigerant, the hydrate is cooled to about −25 ° C. to −20 ° C., which is a low temperature below the freezing point that does not decompose even under low pressure, and is discharged from the hydrate discharge port 32 at the rear end of the container body 30. It will be.

  Therefore, the hydration dehydration step S3 is performed at the front end portion upstream of the container body 30, and the cooling step S4 is performed from the leading end portion to the rear end portion, and the hydration dehydration step S3 is performed in the container body 30. The process of the cooling step S4 is continuously performed while being controlled at an appropriate temperature by a common cooling means.

  Next, FIG. 6 is a production equilibrium diagram of a hydrate produced by reacting water and natural gas. The horizontal axis represents temperature and the vertical axis represents pressure.

  A hatched portion H1 shown in the figure indicates a state where the hydrate generated in the generation step S1 is physically dehydrated in the physical dehydration step S2, the temperature is about 0 ° C. to 5 ° C., and the pressure is higher than the hydrate generation pressure. It is maintained at about 5 MPa.

  A hatched portion H2 indicates a state in which the hydrate dehydrated in the physical dehydration step S2 is reacted with natural gas in the hydration dehydration step S3 to hydrate and dehydrate the residual water contained in the hydrate. The temperature is maintained at about −5 ° C. to 0 ° C., and the pressure is maintained at about 5 MPa.

  A hatched portion H3 indicates a state in which the hydrate dehydrated and dehydrated in the hydration dehydration step S3 is cooled to a low temperature below the freezing point that is not decomposed even under a low pressure in the cooling step S4, and the temperature ranges from −25 ° C. to −20. The pressure is maintained at about 5 ° C. and about 5 MPa.

  The hatched portion H4 indicates a state in which the hydrate cooled in the cooling step S4 is depressurized to about 0.1 MPa while maintaining the temperature at about −25 ° C. to −20 ° C.

  As indicated by the hatched portion H1 in FIG. 6, the temperature of the hydrate that has been physically dehydrated is about 0 ° C. to 5 ° C. When this is cooled slightly under the same pressure, the temperature immediately increases as indicated by the hatched portion H2. Becomes hydrated and dehydrated hydrate at about -5 ° C to 0 ° C.

  Therefore, as shown in FIG. 1, the hydration dehydration step S3 is performed in a short section of the tip portion, which is the first stage in which the physically dehydrated hydrate moves in the container body 30 in the axial direction, and the cooling step S4 is performed thereafter. Hydrate is done in a long section where it moves to the rear end.

  FIG. 2 is an explanatory diagram showing the configuration of the hydrate treatment apparatus according to the second embodiment of the present invention. Like the embodiment shown in FIG. 1, the hydration dehydration step S3 and the cooling step S4 shown in FIG. 7 are performed. In the figure, the same parts as those in the hydrate processing apparatus shown in FIG. 1 are denoted by the same reference numerals, and redundant description is omitted.

  In the first embodiment shown in FIG. 1, the transport mixing means 35 has a rotating shaft 34 with paddles 33 attached at intervals in the axial direction, whereas in this embodiment, a ribbon instead of the paddles 33 is used. 42, and the transfer mixing means 35 is configured to have a rotating shaft 34 to which a ribbon 42 is attached at an interval in the axial direction, and other configurations are the same as those shown in FIG. Yes.

  Accordingly, also in the present embodiment, as in the first embodiment shown in FIG. 1, the hydrate supplied from the hydrate supply port 31 to the tip of the container body 30 is hydrated by the ribbon 42 inside the container body 30. Are mixed while being transported in the axial direction, and in contact with the gas containing the hydrate-forming substance supplied from the gas supply port 37 at the tip of the container body 30 and stirred at a temperature suitable for the hydration reaction. When it is cooled to about −5 ° C. to 0 ° C., it reacts with moisture remaining in the hydrate to be dehydrated, gradually cooled from the front end to the rear end, and stirred while being transferred. By the heat of vaporization of the refrigerant supplied to the refrigerant space 38, the hydrate is cooled to about −25 ° C. to −20 ° C., which is a low temperature below the freezing point that does not decompose even under low pressure, and the rear end of the container body 30 And it is discharged from the hydrate outlet 32 in.

  Also in this embodiment, as shown in FIG. 2, the hydration dehydration step S3 is performed in a short section of the tip, which is the first stage in which the physically dehydrated hydrate moves in the container body 30 in the axial direction, and the cooling step S4. After that, the hydrate is performed in a long section where the hydrate moves to the rear end.

  Thus, in the hydrate treatment apparatus of Example 1 shown in FIG. 1 and Example 2 shown in FIG. 2, hydration dehydration and cooling were supplied to the refrigerant space 38 provided on the outer periphery of the container body 30. Since it is made in the same container body 30 by the refrigerant, there is no need to separately provide a hydration dehydration device and a cooling device and drive them by separate drive units, or separately provide cooling means for hydration dehydration and cooling. The apparatus configuration is simple and can be made compact, and the processing apparatus can be manufactured at low cost, which is very convenient.

  Further, in the first embodiment and the second embodiment, if the hydrate supply port 31 and the gas supply port 37 are not provided separately, and they are made common, the device configuration is simpler and more compact, A processing apparatus can be manufactured at low cost.

  In addition, in the container main body 30, as the transfer mixing means 35 for mixing while transferring in the axial direction, in the first embodiment, the transfer mixing means 35 having the rotating shaft 34 to which the paddles 33 are attached at intervals in the axial direction. In the second embodiment, the transfer mixing means 35 having the rotating shaft 34 with the ribbons 42 attached at intervals in the axial direction is used as a paddle type transfer mixer or a ribbon type transfer mixer. Can be manufactured and handled easily, and can be manufactured at a lower cost. However, as long as it has a function of mixing while transporting in the axial direction, it can be transported using another structure. Also good.

  Moreover, in the said Example 1 and Example 2, although the container main body 30 is made into cylindrical shape, according to the structure of the transfer mixing means accommodated in the container main body 30, the container main body 30 is made into shapes other than cylindrical shape. Also good.

  In the first embodiment and the second embodiment, the rotation shaft 34 of the transfer and mixing means 35 accommodated in the container main body 30 is a single shaft. However, the container main body 30 is formed into an oval cylindrical shape, and the container main body 30 A transfer mixing means 35 having a plurality of rotating shafts 34 may be provided therein to efficiently process a large amount of hydrate.

  In the first embodiment and the second embodiment, the refrigerant in the refrigerant space 38 is extracted from the front end side of the container body 30 and circulated to the rear end side while being transported in the container body 30 in the axial direction. The refrigerant circulation rate is appropriately controlled so that the hydrate to be mixed is gradually cooled from about −5 ° C. to 0 ° C. to about −25 ° C. to −20 ° C. from the front end to the rear end. However, the refrigerant space 38 is divided into a front end side of a short section corresponding to the hydration dehydration step S3 and a rear end side of a long section corresponding to the cooling process S4, and the refrigerant space 38 is divided into the partitioned refrigerant space 38, respectively. It is also possible to supply the refrigerant separately and control the refrigerant to have an appropriate temperature.

  FIG. 3 is an explanatory diagram showing the configuration of a hydrate treatment apparatus according to Embodiment 3 of the present invention, which performs the physical dehydration step S2, the hydration dehydration step S3, and the cooling step S4 shown in FIG. The same parts as those in the hydrate treatment apparatus that performs the processes of the hydration and dehydration step S3 and the cooling step S4 shown in FIG.

  In the figure, reference numeral 10 denotes a screw press type dewatering device. A cylindrical screen (mesh) -shaped filter medium 12 and a large number of rods on the rear end side are cylindrically formed along the circumference inside a main body having a cylindrical inner space. The filter medium 12a is arranged, a screw rotating shaft 13 which is a shaft body having a spiral protrusion on the side surface and disposed in the internal space, and a drive unit 14 for driving the screw rotating shaft 13.

  Further, as shown in FIG. 8, the hydrate and water slurry generated in the generation container 1 is extracted by a slurry extraction pump 11 and supplied to the tip of a screw press type dehydrator 10 via a slurry pipe 9. It has come to be.

  The slurry of hydrate and water supplied to the tip of the screw press type dehydrator 10 is driven to the rear end by a spiral protrusion by driving a drive unit 14 attached to the tip of the screw rotating shaft 13. The screw press type dehydrating apparatus 10 is provided on the rear end surface of the screw press type dehydrating apparatus 10 after being axially transferred and squeezed and physically dehydrated by a squeezed portion 13 a having a tapered diameter at the rear end of the screw rotating shaft 13. From the opening 10a for hydrate discharge | emission, it is comprised so that it may discharge | emit back in the state which filled the opening 10a.

  The water physically dehydrated by the screw press type dehydrator 10 is filtered by the filter media 12 and 12 a, extracted from the bottom of the main body on the tip side of the screw press type dehydrator 10, and formed through a water pipe 16. 1 is returned.

  1 is connected to the rear end of the screw press type dehydrating apparatus 10 to perform the processes of the hydration dehydrating process S3 and the cooling process S4 shown in FIG. Is provided with an opening 30a in place of the hydrate supply port 31 at the front end surface of the container body 30 of the hydrate treatment apparatus, and the opening 10a provided on the rear end face of the screw press type dehydrator 10 and the container. An opening 30a provided on the front end surface of the main body 30 is communicated.

  Further, the screw rotating shaft 13 of the screw press type dehydrating apparatus 10 and the rotating shaft 34 of the transfer mixing means 35 housed in the container body 30 are connected, and when the drive unit 14 is driven, the screw of the screw press type dehydrating apparatus 10 is connected. The rotary shaft 13 and the rotary shaft 34 of the transfer mixing means 35 are driven by a common drive unit 14.

  In addition, since the other structure of the container main body 30 is the same as what is shown in FIG. 1, description is abbreviate | omitted.

  Therefore, in this embodiment, the hydrate and water slurry supplied to the tip of the screw press dehydrator 10 is physically dehydrated by the screw press dehydrator 10 by driving the drive unit 14. The container main body passes through the opening 30a provided on the front end surface of the container main body 30 communicating with the hydrate discharge opening 10a from the hydrate discharge opening 10a provided on the rear end face of the screw press type dehydrator 10. Since it is continuously supplied into the interior 30, the physical dehydration step S2, the hydration dehydration step S3, and the cooling step S4 are continuously performed as shown in the figure.

  FIG. 4 is an explanatory diagram showing the configuration of the hydrate treatment apparatus according to Embodiment 4 of the present invention. Like the embodiment shown in FIG. 3, the physical dehydration step S2, the hydration dehydration step S3 and the cooling step shown in FIG. The processing of S4 is performed, and the same parts as those in the hydrate processing apparatus shown in FIG.

  In the embodiment shown in FIG. 3, the process of the hydration dehydration step S3 and the cooling step S4, in which the transfer mixing means 35 having the rotating shaft 34 with the paddles 33 attached in the axial direction is accommodated, is performed in FIG. The screw press type dehydrating apparatus 10 that performs the process of the physical dehydration step S2 is connected to the tip of the container body 30 shown so that the processes of the physical dehydration process S2, the hydration dehydration process S3, and the cooling process S4 are performed continuously. However, the present embodiment is shown in FIG. 2 for carrying out the processes of the hydration dehydration step S3 and the cooling step S4 in which the transfer mixing means 35 having the rotating shaft 34 with the ribbons 42 attached in the axial direction is accommodated. A screw press type dehydrating apparatus 10 for performing the physical dehydration step S2 is connected to the tip of the container body 30, and the physical dehydration step S2, the hydration dehydration step S3, and the hydration dehydration are performed in the same manner as in Example 3 shown in FIG. Craft Processing at S3 is that so as to be continuously made.

  As described above, in Example 3 shown in FIG. 3 and Example 4 shown in FIG. 4, hydrate physical dehydration, hydration dehydration, and cooling can be continuously performed in direct communication, and the apparatus configuration is further improved. It is simpler and more compact, and the processing apparatus can be manufactured at low cost.

  In Example 3 and Example 4 described above, the screw press type dehydrating apparatus 10 that is generally used as a physical dehydrating apparatus can be used. However, if it is a physical dehydration device having an opening 10a communicating with an opening 30a provided on the front end surface of the container body 30 for performing the hydration dehydration step S3 and the cooling step S4 on the rear end surface, a screw press type dehydration is possible. A physical dehydration apparatus other than the apparatus 10 may be used.

  The hydrate that has been physically dehydrated in the physical dehydration step S2 is controlled to have a temperature of about 0 ° C. to 5 ° C. as indicated by the hatched portion H1 in FIG. For example, the refrigerant pipe 39 of the refrigerant supplied to the refrigerant space 38 of the container main body 30 that performs the processes of the hydration dehydration step S3 and the cooling step S4 is branched and provided inside the screw rotating shaft 13 of the screw press type dehydrator 10. Alternatively, the coolant may be guided to a cooling passage (not shown) to appropriately cool the internal space of the screw press type dehydrator 10.

  In Examples 1 to 4, the physical dehydration step S2, the hydration dehydration step S3, and the cooling step S4 are all processed under a pressure of about 5 MPa as shown in FIG. The pressure of about 5 MPa is maintained in the screw press type dehydrator 10 for performing the physical dehydration step S2 and the container body 30 for performing the hydration dehydration step S3 and the cooling step S4. Appropriate sealing means, not shown, are provided to obtain.

  Moreover, in Example 3 and Example 4, since the screw rotating shaft 13 of the screw press type | mold dehydrator 10 and the rotating shaft 34 of the transfer mixing means 35 accommodated in the container main body 30 are connected integrally, screw The screw rotating shaft 13 of the press type dehydrating apparatus 10 and the rotating shaft 34 of the transfer mixing means 35 can be driven by a common drive unit 14, and the processing apparatus can be manufactured at a lower cost. The screw rotating shaft 13 of the ten and the rotating shaft 34 of the transfer mixing means 35 are detachably connected, and the container body 30 and the screw press type dehydrator 10 connected to each other are also detachably connected so that disassembly and repair are easy. You may be able to do it.

  However, since the rotary shaft 34 of the transfer mixing means 35 has a smaller diameter than the screw rotary shaft 13 of the screw press type dehydrator 10, when the connected screw rotary shaft 13 and the rotary shaft 34 are long, The vicinity of the connecting portion may be pivotally supported in consideration of not causing much obstacle to the transfer of the hydrate to be transferred.

  Moreover, in Example 3 and Example 4, if the screw rotating shaft 13 of the screw press type | mold dehydrator 10 and the rotating shaft 34 of the transfer mixing means 35 are made into two or more, a large amount of hydrates can be processed efficiently.

  FIG. 5 is an explanatory diagram showing a partial configuration of a hydrate processing apparatus according to Embodiment 5 of the present invention.

  FIG. 5 shows the configuration of the distal end portion of the container body 30 shown in FIG. 1 or 2, and the hydrate supply port 31 common to the gas supply port 37 is provided at the distal end portion of the container body 30. The rotation shaft 34 of the transfer mixing means 35 housed in the container body 30 is driven by a drive unit 36.

  Reference numerals 43 and 44 denote arms that support the paddle 33 shown in FIG. 1 or the ribbon 42 shown in FIG. 2, and are attached to the rotary shaft 34 at intervals in the axial direction. The arm 44 of the paddle 33 or ribbon 42 near the hydrate supply port 31 is shorter than the length of the arm 43 of the other paddle 33 or ribbon 42, and the length of the arm 44 is longer along the hydrate transfer direction. After the length becomes the same as that of the arm 43, the length is constant.

  Since the hydrate supplied from the hydrate supply port 31 is not solidified due to moisture solidification, it adheres to the wall surface and tends to solidify. Therefore, the paddle 33 or the ribbon 42 near the hydrate supply port 31 If the length of the arm 44 is long, the hydrate is rubbed against the wall surface at the portion indicated by A in the figure, and the hydrate is blocked because it is not stirred well.

  However, if the length of the arm 44 of the paddle 33 or ribbon 42 near the hydrate supply port 31 is shorter than the length of the arm 43 of the other paddle 33 or ribbon 42, the hydrate is transferred from the hydrate supply port 31 into the container body 30. Since the stirring and cooling can be started from the state where the hydrate is dropped and piled up on the portion indicated by B in the figure, the hydrate is prevented from being blocked and a large amount of hydrate is efficiently produced. Can be processed.

  In addition, although water contained in the hydrate may become ice in a short time at the hydrate supply port 31 and the hydrate may be blocked, a heating facility such as a heat trace is provided at the hydrate supply port 31 to heat the hydrate. If heating is performed by the facility, hydrate blockage in the vicinity of the hydrate supply port 31 is prevented, and a large amount of hydrate can be processed efficiently.

  In addition, if a scraping device is provided at the hydrate supply port 31 and the ice and hydrate blocked by the scraping device are scraped off, the hydrate blockage near the hydrate supply port 31 is prevented, and a large amount of Hydrate can be processed efficiently.

  Also, if the hydrate supply port 31 is lined with a resin having a low coefficient of friction such as Teflon (registered trademark), the hydrate supply port 31 is difficult to adhere to the hydrate supply port 31, and the hydrate is prevented from being clogged. Can be processed well.

  Further, if the paddle 33 and the ribbon 42 are lined with a resin having a low friction coefficient such as Teflon (registered trademark), the paddle 33 and the ribbon 42 are hardly adhered to the paddle 33 and the ribbon 42, and the hydrate is prevented from being blocked. Can be processed well.

  In addition, you may provide each said means to prevent the obstruction | occlusion of a hydrate independently or in combination as needed.

  As mentioned above, although this invention was demonstrated based on Examples 1-5 shown in FIGS. 1-5, according to this invention, the processing apparatus of the hydrate produced | generated by making the gas containing water and a hydrate formation substance react The device configuration is simple, can be made compact and can be manufactured at low cost, the running cost is low, the hydrate processing efficiency can be improved, the handling is easy and the conventional problems can be solved, A hydrate processing apparatus that is extremely effective in practical use can be provided.

  However, the present invention is not limited to the above-described embodiments, and the configuration and driving method of the physical dehydration apparatus to be used, the transport mixing means housed in the container body for performing hydration dehydration and cooling, and the hydrate It goes without saying that various means may be added to the specific structure of the means for preventing the blockage within the scope of the present invention, depending on the required processing capacity and additional functions.

It is explanatory drawing which shows the structure of the hydrate processing apparatus which concerns on Example 1 of this invention. It is explanatory drawing which shows the structure of the hydrate processing apparatus which concerns on Example 2 of this invention. It is explanatory drawing which shows the structure of the hydrate processing apparatus which concerns on Example 3 of this invention. It is explanatory drawing which shows the structure of the hydrate processing apparatus which concerns on Example 4 of this invention. It is explanatory drawing which shows the structure of a part of hydrate processing apparatus which concerns on Example 5 of this invention. It is a production | generation equilibrium diagram of the hydrate produced | generated by making water and natural gas react. It is process drawing which shows an example of the conventional hydrate manufacturing process. It is explanatory drawing which shows the structure of the production | generation process S1, the physical dehydration process S2, the hydration dehydration process S3, and the cooling process S4 shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Generation container 2 Water piping 3 Gas piping 4 Water piping 5 Water circulation pump 6 Heat exchanger 7 Spray nozzle 8 Slurry extraction outlet 9 Slurry piping 10 Screw press type dehydrating apparatus 10a Opening 11 Slurry extraction pump 12 Filter medium 12a Filter medium 13 Screw rotation shaft 13a Squeeze unit 14 Drive unit 15 Hydrate discharge pipe 16 Water pipe 17 Twin screw type dehydrator 18 Screw rotary shaft 19 Drive unit 20 Gas pipe 21 Hydrate discharge pipe 22 Screw conveyor type cooling device 23 Screw rotary shaft 24 Drive unit 25 Hydrate discharge pipe 26 Refrigerant space 27 Refrigerant pipe 28 Refrigerant circulation pump 29 Heat exchanger 30 Container body 30a Opening 31 Hydrate supply port 32 Hydrate discharge port 33 Paddle 34 Rotating shaft 35 Transfer mixing means 36 Drive unit 37 Gas supply Mouth 38 coolant space 39 refrigerant pipe 40 refrigerant circulation pump 41 heat exchanger 42 ribbon 43 arm 44 arm (hydrate supply opening neighborhood)
G gas phase L liquid phase S1 generation process S2 physical dehydration process S3 hydration dehydration process S4 cooling process S5 decompression process S6 molding process

Claims (15)

  The front end of the container body has a hydrate supply port for supplying hydrate at the front end and a hydrate discharge port for discharging hydrate at the rear end. A gas supply port for supplying a gas containing a hydrate-forming substance is provided in the section, and a refrigerant space is provided on the outer periphery of the container body so that a cooling refrigerant is supplied into the refrigerant space. Hydrate processing device.   The hydrate processing apparatus according to claim 1, wherein the hydrate supply port and the gas supply port are common.   The hydrate processing apparatus according to claim 1 or 2, wherein the transfer mixing means has a rotating shaft with paddles attached at intervals in the axial direction.   The hydrate processing apparatus according to claim 1 or 2, wherein the transfer and mixing means has a rotating shaft to which a ribbon is attached at an interval in the axial direction.   The hydrate processing apparatus according to any one of claims 1 to 4, wherein a hydrate supply port provided at a tip portion of the container body is an opening provided at a tip surface of the container body, and the hydrate is passed through the opening. A hydrate treatment apparatus characterized in that it is communicated with a hydrate discharge opening provided on a rear end surface of a physical dehydration apparatus that physically dehydrates the hydrate.   6. The hydrate treatment apparatus according to claim 5, wherein the physical dehydrator is a screw press type dehydrator.   7. The hydrate processing apparatus according to claim 6, wherein the screw rotating shaft of the screw press type dehydrating device and the rotating shaft of the transfer and mixing means are connected and driven by a common drive unit. Processing equipment.   8. The hydrate processing apparatus according to claim 7, wherein the screw rotating shaft of the screw press type dehydrating device and the rotating shaft of the transfer and mixing means are plural.   The hydrate processing apparatus according to any one of claims 1 to 4, wherein a heating facility is provided at the hydrate supply port.   The hydrate processing apparatus according to any one of claims 1 to 4, wherein a scraping device is provided at the hydrate supply port.   The hydrate processing apparatus according to any one of claims 1 to 4, wherein the hydrate supply port is lined.   4. The hydrate processing apparatus according to claim 3, wherein the length of the arm of the paddle near the hydrate supply port is made shorter than the length of the arm of the other paddle.   4. The hydrate processing apparatus according to claim 3, wherein the paddle is lined.   5. The hydrate processing apparatus according to claim 4, wherein the length of the ribbon arm near the hydrate supply port is shorter than the length of the other ribbon arm.   The hydrate processing apparatus according to claim 4, wherein the ribbon is lined.

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