CN111849574A - Device and method for storing and transporting natural gas based on hydrate method - Google Patents
Device and method for storing and transporting natural gas based on hydrate method Download PDFInfo
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- CN111849574A CN111849574A CN202010699252.3A CN202010699252A CN111849574A CN 111849574 A CN111849574 A CN 111849574A CN 202010699252 A CN202010699252 A CN 202010699252A CN 111849574 A CN111849574 A CN 111849574A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/108—Production of gas hydrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
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Abstract
The invention provides a device and a method for storing and transporting natural gas based on a hydrate method, which can realize solid storage and transportation of natural gas and acid gas and H in associated condensate gas by designing a natural gas acid gas separation unit and a natural gas hydrate preparation unit and adopting a hydration method to carry out solid storage and transportation of natural gas2And the method provides a theoretical basis for further realizing the industrial application of the hydrate method and has important practical significance for the popularization and application of hydrate storage and transportation technology.
Description
Technical Field
The invention relates to the field of natural gas storage and transportation, in particular to a device and a method for storing and transporting natural gas based on a hydrate method.
Background
With the rapid development of economy in China, the consumption of natural gas in the industrial aspect and the civil aspect is rapidly increased, which prompts the large-scale development of natural gas fields in vast outlying areas and on the sea. The storage and transportation of natural gas from these fields is challenging due to geographical and environmental factors. The traditional natural gas storage and transportation modes mainly include pipeline transportation and LNG modes, but pipeline laying and maintenance, LNG preparation and storage have the defects of huge investment, high cost and the like. In addition, many oil fields in China have a large amount of associated condensate gas, and are limited by storage and transportation economy, and the common treatment mode is to send the associated condensate gas to an overhead flare tower for combustion, so that resources are wasted, and the environment is polluted. It is against this background that natural gas hydrate technology has emerged. Natural gas hydrate technology is the conversion of natural gas from a gaseous state to a solid hydrate form, making it convenient to transport and reconvert to gaseous natural gas. Because the natural gas storage and transportation cost is obviously reduced, the economy and the safety of natural gas storage and transportation are improved, and the natural gas storage and transportation method is generally regarded by the industry.
Compared with other storage and transportation modes of natural gas, the hydrate storage and transportation natural gas has the advantages of simple process flow, safe technology, lower economic cost and the like compared with other storage and transportation modes. The hydrate has an adiabatic effect, so even if the hydrate is exposed to the atmosphere, the decomposition of the hydrate is influenced by heat conduction, the release rate of the gas is slow, and the gas can be slowly combusted even if the hydrate is ignited, thereby thoroughly inhibiting the possible explosion accidents caused by the large leakage of the natural gas. And the hydrate storage and transportation mode at the middle distance is the most economical compared with the pipeline transportation. However, the technology for storing and transporting natural gas by a hydration method starts late, and some technical problems such as efficient hydrate production process, optimization of hydrate generation conditions (pressure, temperature and accelerant) and the like are not solved yet.
Therefore, a device and a method for storing and transporting natural gas based on a hydrate method are needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects of the prior art, the invention provides the device and the method for storing and transporting the natural gas by using the hydrate method, which have simple process and high production efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows: a device for storing and transporting natural gas based on a hydrate method comprises a natural gas acid gas separation unit and a natural gas hydrate preparation unit;
The natural gas acid gas separation unit comprises a raw gas storage tank, an inlet separator and an absorption tower which are sequentially connected through pipelines, the top of the absorption tower is connected with the outlet separator, an outlet of the outlet separator is communicated with the natural gas hydrate preparation unit, and the absorption tower is further connected with an acid gas treatment unit;
the natural gas hydrate preparation unit comprises a water storage tank, an ice water preparation device, a low-pressure hydration reaction tank group, a separation tank and a hydrate storage tank which are sequentially communicated through pipelines, wherein an inlet of the ice water preparation device is further connected with an accelerator storage tank, an ice water recovery port is formed in the bottom of the separation tank, the ice water recovery port is communicated with a water inlet of the ice water preparation device, an outlet of an outlet separator is connected with an inlet of the low-pressure hydration reaction tank group, and a top outlet of the low-pressure hydration reaction tank group is communicated with a hydrogen concentrator.
Furthermore, the low-pressure hydration reaction tank group comprises a first low-pressure hydration reaction tank, a second low-pressure hydration reaction tank and a third low-pressure hydration reaction tank; the outlet of the outlet separator is respectively connected with the lower inlets of the first low-pressure hydration reaction tank and the second low-pressure hydration reaction tank, and the upper inlet of the first low-pressure hydration reaction tank is connected with the outlet of the ice water preparation device; the bottom outlet of the first low-pressure hydration reaction tank is connected with the upper inlet of the second low-pressure hydration reaction tank, and the top outlet of the first low-pressure hydration reaction tank is connected with the lower inlet of the second low-pressure hydration reaction tank; the top outlet of the second low-pressure hydration reaction tank is connected with the lower inlet of the third low-pressure hydration reaction tank, the bottom outlet of the second low-pressure hydration reaction tank is connected with the upper inlet of the third low-pressure hydration reaction tank, and the bottom outlet of the third low-pressure hydration reaction tank is connected with the separation tank.
Further, the acid gas treatment unit comprises a flash tank, a filter, a lean rich liquor heat exchanger, a regeneration tower, a reflux collector, a reboiler and a buffer tank; a rich liquid outlet at the bottom of the absorption tower is connected with an inlet of the flash tank, an outlet of the flash tank is connected with an upper inlet of the filter, a lower outlet of the filter is connected with an upper inlet of the regeneration tower, and the connected pipeline passes through the lean rich liquid heat exchanger; the bottom outlet of the regeneration tower is connected with the inlet of the reboiler; an upper outlet of the reboiler is connected with a lower inlet of the regeneration tower, a lower outlet of the reboiler is connected with an upper inlet of the absorption tower, the connecting pipeline passes through the lean rich liquid heat exchanger, and the buffer tank is connected to a connecting pipeline between the lower outlet of the reboiler and the lean rich liquid heat exchanger.
Further, 14 layers of tower plates are arranged in the absorption tower, and a temperature sensor and a pressure sensor are arranged on the absorption tower; 18 layers of tower plates are arranged in the regeneration tower, and a temperature sensor and a pressure sensor are arranged on the regeneration tower; pressure sensors are arranged on the reboiler and the reflux collector; all related liquid phase conveying pipelines in the acid gas treatment unit are provided with liquid pressure regulating valves; and a gas flowmeter is arranged on an input pipeline of the acid gas collector.
Furthermore, the first low-pressure hydration reaction tank, the second low-pressure hydration reaction tank and the third low-pressure hydration reaction tank have the same structure, the top parts of the first low-pressure hydration reaction tank, the second low-pressure hydration reaction tank and the third low-pressure hydration reaction tank are respectively provided with a temperature sensor, the tank wall of the tank body is of a double-layer structure, a refrigerating device is arranged in the middle of the double-layer structure, and a spiral tower plate is arranged in the tank body; when the reaction is carried out in the tank body, gas-liquid two phases are in countercurrent contact, an ice-water mixture generated by the ice-water preparation device enters from an inlet at the upper part of the tank body, and a gas phase enters from an inlet at the lower part of the tank body; a safety valve is arranged at an outlet at the top of the tank body; a gas flowmeter is also arranged on the top outlet of the third low-pressure hydration reaction tank; the gas phase pipelines of the low-pressure hydration reaction tank group are all provided with gas regulating valves, and the liquid phase conveying pipelines are all provided with liquid circulating pumps.
Preferably, in the natural gas hydrate preparation unit, the working pressure range is normal pressure, and the temperature is-15 ℃; the ice water proportion in the ice water preparation device is 1: 1; the compound accelerator in the accelerator storage tank is carbon dioxide nanotube O-CNTS and Sodium Dodecyl Sulfate (SDS), and the addition concentration is as follows: the concentration of the oxidized carbon nanotube aqueous solution is 1g/L, and the concentration of the sodium dodecyl sulfate aqueous solution is 230.704 mg/L; the solution used in the natural gas acid gas separation unit is diethanolamine DEA solution.
Preferably, the temperature of the solution in the absorption tower is controlled to be 46-46.5 ℃, and the pressure is controlled to be 3.9-4.0 MPa; the pressure of the flash tank is controlled to be 0.6 MPa; the inlet temperature of the regeneration tower is 90 ℃, the outlet temperature is 123 ℃, and the pressure is 0.6 MPa; the reboiler pressure was set at 210kpa and the reflux accumulator pressure at 180 kpa.
A device for storing and transporting natural gas based on a hydrate method comprises the following use methods:
a. in the natural gas-acid gas separation unit, raw gas of a raw material gas tank enters an inlet separator, is separated and then is sent into an absorption tower, two streams are obtained after reaction in the absorption tower, and one mixed gaseous stream which is led out from the top of the absorption tower and consists of methane and hydrogen enters an outlet separator and enters a hydrate preparation unit; the other strand is treated by the residual solution after the reaction in the reaction device through an acid gas treatment unit;
b. in the natural gas hydrate preparation unit, mixing water from a water storage tank and a hydrate accelerator in proportion, feeding the mixed solution into an ice water preparation device, pumping the prepared ice water mixture solution into a low-pressure hydration reaction tank group through a solution pump, reacting with incoming gas prepared by an acid gas separation unit to form a mixed solution of hydrate and ice water, and after the reaction is finished, remaining H after the reaction 2Flowing to a hydrogen-rich collector from the tower top, and allowing all the residual mixed liquid of the hydrate, ice water and the hydrate to flow out from the bottom of the reaction tower and enter a separator; and the natural gas hydrate solid is separated by the separator and enters a hydrate storage tank, and the mixture of the residual ice water and the accelerator is output from an outlet at the bottom of the separator and flows into an ice water preparation device.
Further, inIn the natural gas acid gas separation unit, the solution left in the reaction device after the reaction flows into a flash tank, enters a filter from the flash tank, and the filtered solution enters a regeneration tower; the solution entering the regeneration tower is reacted and divided into two streams, one stream is a gaseous stream comprising SO and composed of acid gas led out from the top of the regeneration tower2And CO2The acid gas enters an acid gas collector after passing through a reflux collection tank; and the other reacted solution enters the reboiler from the bottom of the regeneration tower, one part of the solution entering the reboiler is heated and then conveyed back to the regeneration tower, and the other part of the solution is conveyed back to the absorption tower through the solution pump.
Furthermore, in the natural gas hydrate preparation unit, the prepared ice-water mixture solution prepared by the ice-water preparation device is pumped into the first low-pressure hydration reaction tower through a solution pump, and after the ice-water mixture solution reacts with the incoming gas prepared by the acid gas separation unit, the formed mixed solution of the hydrate and the ice water enters from the upper part of the second low-pressure hydration reaction tank through the pump; unreacted gas in the first low-pressure hydration reaction tank flows out from the top of the reaction tank, and is fed into the second low-pressure hydration reaction tank together with incoming gas prepared by the acid gas separation unit from the lower part of the second low-pressure hydration reaction tank, after the reaction process of the second low-pressure hydration reaction tank is finished, the formed mixed solution of hydrate and ice water is pressurized by a pump and is fed into the third low-pressure hydration reaction tank from the upper part of the third low-pressure hydration reaction tank, the unreacted gas in the second low-pressure hydration reaction tank flows out from the top of the reaction tank and is fed into the third low-pressure hydration reaction tank from the lower part of the third low-pressure hydration reaction tank, and after 2And the residual mixed liquid of all the hydrates, ice water and the hydrates flows out from the bottom of the reaction tank and enters a separator.
The invention has the beneficial effects that:
(1) in the hydrate preparation unit, the working pressure range is normal pressure, and the temperature is-15 ℃, so the production link is safe and reliable.
(2) The invention adopts the compound accelerant mixed by the carbon oxide nanotube and the sodium dodecyl sulfate and is matched with the three-stage reactor system, thereby greatly improving the generation efficiency of the hydrate and reducing the energy consumption; the compound accelerator is environment-friendly and pollution-free, and does not generate corrosive harm to equipment; and the oxidized carbon nanotube is a recyclable accelerant, so that the production cost of the hydrate is greatly reduced.
(3) The invention adopts the hydrate method to store and transport the natural gas, and can independently purify and collect H in the gas mixture while preparing the natural gas hydrate2. The device and the method have important significance for popularization of the hydration method in actual production, and provide important reference for process flow design of hydrate storage, transportation and storage technologies.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a schematic structural diagram of the preferred embodiment of the present invention.
In the figure, 1, an accelerator storage tank 2, an ice water preparation device 3, an outlet separator 4, an absorption tower 5, an inlet separator 6, a flash tank 7, a filter 8, a regeneration tower 9, a reboiler 10, a buffer tank 11-1, a first low-pressure hydration reaction tank 11-2, a second low-pressure hydration reaction tank 11-3, a third low-pressure hydration reaction tank 12, a separation tank 13, a safety valve 14, an ice water recovery port 15, a reflux collection tank 16, a check valve 17, a hydrogen enricher 18, an acid gas collector 19, a water storage tank 20, a hydrate storage tank 21, a feed gas storage tank 22, a lean liquid cooler 23, a lean liquid circulating pump 24, a solution pump 25, a lean and rich liquid heat exchanger 26, a gas flowmeter 27, a gas regulating valve 28, a liquid pressure regulating valve 29, a temperature sensor 30, a pressure sensor 31, a gas pressure sensors, A liquid circulation pump.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. The drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner and thus show only the constitution related to the present invention.
Fig. 1 shows an apparatus and a method for storing and transporting natural gas based on a hydrate method, which are preferred embodiments of the present invention. The device comprises a natural gas acid gas separation unit and a natural gas hydrate preparation unit.
The natural gas acid gas separation unit comprises a raw material gas storage tank 21, an inlet separator 5 and an absorption tower 4 which are sequentially connected through a pipeline, the top of the absorption tower 4 is connected with an outlet separator 3, an outlet of the outlet separator 3 is communicated with a natural gas hydrate preparation unit, and the absorption tower 4 is further connected with an acid gas treatment unit.
The acid gas treatment unit comprises a flash tank 6, a filter 7, a lean-rich liquid heat exchanger 25, a regeneration tower 8, a reflux collector, a reboiler 9 and a buffer tank 10; a rich liquid outlet at the bottom of the absorption tower 4 is connected with an inlet of a flash tank 6, an outlet of the flash tank 6 is connected with an upper inlet of a filter 7, a lower outlet of the filter 7 is connected with an upper inlet of a regeneration tower 8, and the connected pipeline passes through a lean rich liquid heat exchanger 25; the outlet at the bottom of the regeneration tower 8 is connected with the inlet of the reboiler 9; an upper outlet of the reboiler 9 is connected with a lower inlet of the regeneration tower 8, a lower outlet of the reboiler 9 is connected with an upper inlet of the absorption tower 4, the connected pipeline passes through the lean rich liquid heat exchanger 25, and the buffer tank 10 is connected with a lower outlet of the reboiler 9 and a connecting pipeline of the lean rich liquid heat exchanger 25. A lean liquid cooler 22 and a lean liquid circulating pump 23 are further arranged on a pipeline between the lean-rich liquid heat exchanger 25 and an upper inlet of the absorption tower 4.
The absorption tower 4 is internally provided with 14 layers of tower plates, and the absorption tower 4 is provided with a temperature sensor 29 and a pressure sensor 30. The temperature of the solution in the absorption tower 4 is controlled to be 46-46.5 ℃, and the pressure is controlled to be 3.9-4.0 MPa. The pressure of the flash tank 6 is controlled to be 0.6MPa, 18 layers of tower plates are arranged in the regeneration tower 8, a temperature sensor 29 and a pressure sensor 30 are arranged on the regeneration tower 8, the inlet temperature of the regeneration tower 8 is 90 ℃, the outlet temperature is 123 ℃, and the pressure is 0.6 MPa. The pressure sensors 30 are arranged on the reboiler 9 and the reflux collector, the pressure of the reboiler 9 is set to 210kpa, and the pressure of the reflux collection tank 15 is set to 180 kpa. All related liquid phase conveying pipelines in the acid gas treatment unit are provided with liquid pressure regulating valves 28; the input pipe of the acid gas collector 18 is provided with a gas flow meter 26.
The natural gas hydrate preparation unit comprises a water storage tank 19, an ice water preparation device 2, a low-pressure hydration reaction tank group, a separation tank 12 and a hydrate storage tank 20 which are sequentially communicated through pipelines, an inlet of the ice water preparation device 2 is further connected with an accelerator storage tank 1, an ice water recovery port 14 is formed in the bottom of the separation tank 12, the ice water recovery port 14 is communicated with a water inlet of the ice water preparation device 2, an outlet of an outlet separator 3 is connected with an inlet of the low-pressure hydration reaction tank group, and a top outlet of the low-pressure hydration reaction tank group is communicated with a hydrogen concentrator 17.
The low-pressure hydration reaction tank group comprises a first low-pressure hydration reaction tank 11-1, a second low-pressure hydration reaction tank 11-2 and a third low-pressure hydration reaction tank 11-3; an outlet of the outlet separator 3 is respectively connected with lower inlets of the first low-pressure hydration reaction tank 11-1 and the second low-pressure hydration reaction tank 11-2, and an upper inlet of the first low-pressure hydration reaction tank 11-1 is connected with an outlet of the ice water preparation device 2; the bottom outlet of the first low-pressure hydration reaction tank 11-1 is connected with the upper inlet of the second low-pressure hydration reaction tank 11-2, and the top outlet of the first low-pressure hydration reaction tank 11-1 is connected with the lower inlet of the second low-pressure hydration reaction tank 11-2; the top outlet of the second low-pressure hydration reaction tank 11-2 is connected with the lower inlet of the third low-pressure hydration reaction tank 11-3, the bottom outlet of the second low-pressure hydration reaction tank 11-2 is connected with the upper inlet of the third low-pressure hydration reaction tank 11-3, and the bottom outlet of the third low-pressure hydration reaction tank 11-3 is connected with the separation tank 12.
The structure of the first low-pressure hydration reaction tank 11-1, the structure of the second low-pressure hydration reaction tank and the structure of the third low-pressure hydration reaction tank 11-3 are the same, the top parts of the tank bodies of the first low-pressure hydration reaction tank 11-1, the second low-pressure hydration reaction tank 11-2 and the third low-pressure hydration reaction tank 11-3 are respectively provided with a temperature sensor 29, the tank wall of the tank body is of a double-layer structure, the middle of the double-layer structure is provided with a refrigerating device, and the inside of the tank body is provided with a spiral tower plate; when the reaction is carried out in the tank body, the gas phase and the liquid phase are in countercurrent contact, the ice-water mixture generated by the ice-water preparation device 2 enters from the inlet at the upper part of the tank body, and the gas phase enters from the inlet at the lower part of the tank body; a safety valve 13 is arranged at the outlet of the top of the tank body; a gas flowmeter 26 is also arranged on the top outlet of the third low-pressure hydration reaction tank 11-3; the gas phase pipelines of the low-pressure hydration reaction tank group are all provided with gas regulating valves 27, and the liquid phase conveying pipelines are all provided with liquid circulating pumps 31. Meanwhile, in order to avoid gas phase confluence, a check valve 16 is further arranged on a gas phase pipeline for supplying gas to the low-pressure hydration reaction tank group through the outlet separator 3, and the check valve 16 is also arranged on a gas phase pipeline among the first low-pressure hydration reaction tank 11-1, the second low-pressure hydration reaction tank 11-2 and the third low-pressure hydration reaction tank 11-3, so that gas backflow is avoided.
In the natural gas hydrate preparation unit, the working pressure range is normal pressure, and the temperature is-15 ℃. The ice water ratio in the ice water preparation device 2 is 1: 1. the compound accelerator in the accelerator storage tank 1 is carbon dioxide nanotube O-CNTS and Sodium Dodecyl Sulfate (SDS), and the addition concentration is as follows: the concentration of the oxidized carbon nanotube aqueous solution is 1g/L, and the concentration of the sodium dodecyl sulfate aqueous solution is 230.704 mg/L. The solution used in the natural gas acid gas separation unit is diethanolamine DEA solution.
Based on the device, the method specifically comprises the following use methods:
the raw material gas enters a raw material gas storage tank 21, enters an inlet separator 5, is treated by the inlet separator 5 and then enters an inlet at the lower part of an absorption tower 4, and after the reaction temperature of the absorption tower 4 is 46-46.5 ℃ and the pressure is 3.9-4.0 MPa, gas phase CH4、H2Enters the outlet separator 3 from the outlet at the top of the absorption tower 4.
The reacted rich liquid in the absorption tower 4 flows out from a bottom outlet, is regulated to 0.6MPa by a liquid pressure regulating valve 28, enters a flash tank 6 for flash evaporation, the flashed rich liquid is filtered by a filter 7 and then enters a lean rich liquid heat exchanger 25, the lean liquid enters a regeneration tower 8 when the temperature is increased to 90 ℃, the lean liquid flows out from the bottom of the regeneration tower 8 when the temperature is 90-124 ℃ after the reaction in the regeneration tower 8, enters a reboiler 9, and the operating pressure of the reboiler 9 is 210 kpa.
In the reboiler 9, a part of the barren solution is reheated and then is returned to the regeneration tower 8 through a lower inlet, the other part of the barren solution enters a barren and rich solution heat exchanger 25, the temperature is reduced to 80 ℃ after heat exchange, then the barren solution is input into a barren solution cooler 22, the temperature is cooled to 38 ℃, then the pressure is increased to 4MPa through a barren solution circulating pump 23, and the barren solution is input into the absorption tower 4 through an upper inlet of the absorption tower 4.
The gas phase portion in the absorption tower 4 passes through the reflux collection tank 15 and then enters the acid gas collector 18.
In the process that water from the water storage tank 19) enters the ice water preparation device 2, the concentration of the compound accelerator carbon oxide nanotube aqueous solution in the accelerator storage tank 1 is 1g/L, and the dodecyl sulfurThe sodium acid water solution with the concentration of 230.704mg/L is added with raw material water according to the proportion, and the mixture is prepared into a mixture according to the proportion 1: 1, pumped into the first low-pressure hydration reactor 11-1 by the solution pump 24, and treated by the outlet separator 3 to obtain a mixed gas phase (CH)4、H2) Enters from the lower part of the first low-pressure hydration reaction tank 11-1; after the reaction, the gas phase flows out from the top of the tank and enters the second low-pressure hydration reaction tank 11-2 from the bottom, and the solid-liquid phase is pumped into the second low-pressure hydration reaction tank 11-2 from the bottom of the first reaction tank through a solution pump 24; the process after the reaction is as the first low-pressure hydration reaction tank 11-1, after the reaction in the third low-pressure hydration reaction tank 11-3, the residual gas enters the hydrogen enricher 17 from the top of the tank, the solid-liquid phase is pumped into the separator from the bottom of the tank through the solution pump 24, the natural gas hydrate is conveyed into the hydrate storage tank 20 after the separation, and the residual solution is connected into a pipeline for secondary utilization.
The above preferred embodiments according to the present invention are given as a teaching that various changes and modifications can be made by workers skilled in the art without departing from the scope of the present invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A device based on hydrate method warehousing and transportation natural gas which characterized in that: the system comprises a natural gas acid gas separation unit and a natural gas hydrate preparation unit;
the natural gas acid gas separation unit comprises a raw gas storage tank (21), an inlet separator (5) and an absorption tower (4) which are sequentially connected through pipelines, the top of the absorption tower (4) is connected with an outlet separator (3), an outlet of the outlet separator (3) is communicated with a natural gas hydrate preparation unit, and the absorption tower (4) is also connected with an acid gas treatment unit;
the natural gas hydrate preparation unit comprises a water storage tank (19), an ice water preparation device (2), a low-pressure hydration reaction tank group, a separation tank (12) and a hydrate storage tank (20) which are sequentially communicated through pipelines, the inlet of the ice water preparation device (2) is further connected with an accelerator storage tank (1), the bottom of the separation tank (12) is provided with an ice water recovery port (14), the ice water recovery port (14) is communicated with the water inlet of the ice water preparation device (2), the outlet of the outlet separator (3) is connected with the inlet of the low-pressure hydration reaction tank group, and the outlet of the top of the low-pressure hydration reaction tank group is communicated with a hydrogen concentrator (17).
2. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 1, wherein: the low-pressure hydration reaction tank group comprises a first low-pressure hydration reaction tank (11-1), a second low-pressure hydration reaction tank (11-2) and a third low-pressure hydration reaction tank (11-3); an outlet of the outlet separator (3) is respectively connected with lower inlets of the first low-pressure hydration reaction tank (11-1) and the second low-pressure hydration reaction tank (11-2), and an upper inlet of the first low-pressure hydration reaction tank (11-1) is connected with an outlet of the ice water preparation device (2); the bottom outlet of the first low-pressure hydration reaction tank (11-1) is connected with the upper inlet of the second low-pressure hydration reaction tank (11-2), and the top outlet of the first low-pressure hydration reaction tank (11-1) is connected with the lower inlet of the second low-pressure hydration reaction tank (11-2); the top outlet of the second low-pressure hydration reaction tank (11-2) is connected with the lower inlet of the third low-pressure hydration reaction tank (11-3), the bottom outlet of the second low-pressure hydration reaction tank (11-2) is connected with the upper inlet of the third low-pressure hydration reaction tank (11-3), and the bottom outlet of the third low-pressure hydration reaction tank (11-3) is connected with the separation tank (12).
3. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 1, wherein: the acid gas treatment unit comprises a flash tank (6), a filter (7), a lean-rich liquid heat exchanger (25), a regeneration tower (8), a reflux collector, a reboiler (9) and a buffer tank (10); a rich liquid outlet at the bottom of the absorption tower (4) is connected with an inlet of a flash tank (6), an outlet of the flash tank (6) is connected with an upper inlet of a filter (7), a lower outlet of the filter (7) is connected with an upper inlet of a regeneration tower (8), and the connected pipeline passes through a lean and rich liquid heat exchanger (25); the bottom outlet of the regeneration tower (8) is connected with the inlet of the reboiler (9); an upper outlet of the reboiler (9) is connected with a lower inlet of the regeneration tower (8), a lower outlet of the reboiler (9) is connected with an upper inlet of the absorption tower (4), the connected pipeline passes through the lean rich liquid heat exchanger (25), and the buffer tank (10) is connected with a connecting pipeline of the lower outlet of the reboiler (9) and the lean rich liquid heat exchanger (25).
4. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 3, wherein: 14 layers of tower plates are arranged in the absorption tower (4), and a temperature sensor (29) and a pressure sensor (30) are arranged on the absorption tower (4); 18 layers of tower plates are arranged in the regeneration tower (8), and a temperature sensor (29) and a pressure sensor (30) are arranged on the regeneration tower (8); the reboiler (9) and the reflux collector are both provided with a pressure sensor (30); all related liquid phase conveying pipelines in the acid gas treatment unit are provided with liquid pressure regulating valves (28); and a gas flowmeter (26) is arranged on an input pipeline of the acid gas collector (18).
5. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 1, wherein: the structure of the first low-pressure hydration reaction tank (11-1), the second low-pressure hydration reaction tank (11-2) and the third low-pressure hydration reaction tank (11-3) is the same, the top of the first low-pressure hydration reaction tank (11-1), the top of the second low-pressure hydration reaction tank (11-2) and the top of the third low-pressure hydration reaction tank (11-3) are respectively provided with a temperature sensor (29), the tank wall of the tank body is of a double-layer structure, the middle of the double-layer structure is provided with a refrigerating device, and the inside of the tank body is provided with a spiral tower plate; when the reaction is carried out in the tank body, the gas phase and the liquid phase are in countercurrent contact, the ice-water mixture generated by the ice-water preparation device (2) enters from the inlet at the upper part of the tank body, and the gas phase enters from the inlet at the lower part of the tank body; a safety valve (13) is arranged at an outlet at the top of the tank body; a gas flowmeter (26) is also arranged on the top outlet of the third low-pressure hydration reaction tank (11-3); the gas phase pipelines of the low-pressure hydration reaction tank group are provided with gas regulating valves (27), and the liquid phase conveying pipelines are provided with liquid circulating pumps (31).
6. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 1, wherein: in the natural gas hydrate preparation unit, the working pressure range is normal pressure, and the temperature is-15 ℃; the ice water ratio in the ice water preparation device (2) is 1: 1; the compound accelerator in the accelerator storage tank (1) is carbon dioxide nanotube O-CNTS and Sodium Dodecyl Sulfate (SDS), and the addition concentration is as follows: the concentration of the oxidized carbon nanotube aqueous solution is 1g/L, and the concentration of the sodium dodecyl sulfate aqueous solution is 230.704 mg/L; the solution used in the natural gas acid gas separation unit is diethanolamine DEA solution.
7. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 3, wherein: the temperature of the solution in the absorption tower (4) is controlled to be 46-46.5 ℃, and the pressure is controlled to be 3.9-4.0 MPa; the pressure of the flash tank (6) is controlled to be 0.6 MPa; the inlet temperature of the regeneration tower (8) is 90 ℃, the outlet temperature is 123 ℃, and the pressure is 0.6 MPa; the pressure of the reboiler (9) is set to 210kpa, and the pressure of the reflux collection tank (15) is set to 180 kpa.
8. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 1, wherein: the method comprises the following steps:
a. In the natural gas-acid gas separation unit, raw gas of a raw material gas tank enters an inlet separator (5), is separated and then is sent into an absorption tower (4), two streams are obtained after reaction in the absorption tower (4), and one mixed gas stream which is led out from the top of the absorption tower (4) and consists of methane and hydrogen enters an outlet separator (3) and enters a hydrate preparation unit; the other strand is treated by the residual solution after the reaction in the reaction device through an acid gas treatment unit;
b. in a natural gas hydrate preparation unit, water from a water storage tank (19) is mixed with a hydrate accelerator in proportion, the mixed solution enters an ice water preparation device (2), the prepared ice water mixture solution is pumped into a low-pressure hydration reaction tank group through a solution pump (24), the mixed solution of the hydrate and the ice water is formed after the mixed solution reacts with incoming gas prepared by an acid gas separation unit, and after the reaction is finished, residual H after the reaction2Flowing to a hydrogen-rich collector from the tower top, and leaving all the hydrate, ice water and waterThe mixed liquid of the compounds flows out from the bottom of the reaction tower and enters a separator; the natural gas hydrate solid is separated by the separator and enters a hydrate storage tank (20), and the mixture of the residual ice water and the accelerator is output from an outlet at the bottom of the separator and flows into an ice water preparation device (2).
9. The apparatus for storage and transportation of natural gas based on hydrate method as claimed in claim 3, wherein: the method comprises the following steps:
the remaining solution after the reaction in the reaction device flows into a flash tank (6), enters a filter (7) from the flash tank (6), and the filtered solution enters a regeneration tower (8); the solution entering the regeneration tower (8) is divided into two parts after reaction, and one part of the gas material flow which is composed of acid gas and is led out from the top of the regeneration tower (8) comprises SO2And CO2The acid gas enters an acid gas collector (18) after passing through a reflux collection tank (15); and the other part of the solution after reaction enters a reboiler (9) from the bottom of the regeneration tower (8), one part of the solution entering the reboiler (9) is heated and then is conveyed back to the regeneration tower (8), and the other part of the solution is conveyed back to the absorption tower (4) through a solution pump (24).
10. The apparatus for storage and transportation of natural gas based on hydrate method according to claim 5, characterized in that: the method comprises the following steps:
the prepared ice-water mixture solution prepared by the ice-water preparation device (2) is pumped into the first low-pressure hydration reaction tower through a solution pump (24), and after the ice-water mixture solution reacts with incoming gas prepared by the acid gas separation unit, the formed mixed solution of the hydrate and the ice water enters from the upper part of the second low-pressure hydration reaction tank (11-2) through the pressurization of the pump; unreacted gas in the first low-pressure hydration reaction tank (11-1) flows out through the top of the reaction tank, and is fed into the second low-pressure hydration reaction tank (11-2) together with incoming gas prepared by the acid gas separation unit, after the reaction process of the second low-pressure hydration reaction tank (11-2) is finished, a formed mixed solution of hydrate and ice water is pressurized by a pump and is fed into the third low-pressure hydration reaction tank (11-3) from the upper part, unreacted gas in the second low-pressure hydration reaction tank (11-2) flows out through the top of the reaction tank and is fed into the third low-pressure hydration reaction tank (11-3) from the lower part, and the third low-pressure hydration reaction tank H remained after the reaction in the reaction tank (11-3) is finished2And the residual mixed liquid of all the hydrates, ice water and the hydrates flows out from the bottom of the reaction tank and enters a separator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112608775A (en) * | 2020-12-02 | 2021-04-06 | 常州大学 | Device and method for rapid cycle generation of gas hydrate |
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| CN103160351A (en) * | 2012-01-09 | 2013-06-19 | 中国科学院理化技术研究所 | Method and device for recovering methane in low-concentration coal bed gas by using hydrate method |
| CN103742788A (en) * | 2014-01-13 | 2014-04-23 | 辽宁石油化工大学 | Natural gas transportation method and device thereof based on hydrate technology |
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