CN112961718A

CN112961718A - Hydrate rapid generation device based on phase-change micro-nano fluid under action of magnetic field

Info

Publication number: CN112961718A
Application number: CN202110151589.5A
Authority: CN
Inventors: 吴强; 赵志伟; 吴琼; 张保勇; 张强; 刘传海; 林能宇
Original assignee: Heilongjiang University of Science and Technology
Current assignee: Heilongjiang University of Science and Technology
Priority date: 2021-02-03
Filing date: 2021-02-03
Publication date: 2021-06-15

Abstract

The invention relates to a device for quickly generating a hydrate based on a phase-change micro-nano fluid under the action of a magnetic field, which comprises an electric rotating table, a linear sliding table, clamping devices, magnetic steel, a high-pressure reaction kettle, a constant temperature box and an air compressor, wherein the linear sliding table is rotatably connected to the electric rotating table, a plurality of clamping devices are connected to the linear sliding table at intervals in a sliding manner, the magnetic steel is fixedly connected to the clamping devices, the high-pressure reaction kettle is placed between the clamping devices, and a target solution containing the phase-change micro-nano fluid is injected into the high-pressure; the gas hydrate separation heat and mass transfer device has the advantages that the gas hydrate separation heat and mass transfer process is enhanced by using the Ni-Mn-based phase-change micro-nano particles and combining the action of a rotating magnetic field, and the hydrate generation effect is improved.

Description

Hydrate rapid generation device based on phase-change micro-nano fluid under action of magnetic field

Technical Field

The invention relates to the technical field of gas separation and storage and transportation, in particular to a device for quickly generating hydrates based on phase-change micro-nano fluid under the action of a magnetic field.

Background

At present, the development and utilization of coal mine gas are accelerated, and the method has important significance for ensuring the safe production of coal mines, increasing the supply of clean energy and reducing the emission of greenhouse gas. The gas hydration reaction separation process has the following two main processes:

1. constraints on heat transfer: since the formation of gas hydrates is an exothermic process, the heat generated during nucleation destroys the crystal nuclei, resulting in a slow growth of the crystal structure, in which heat transfer is a very important phenomenon. The hydrate has low heat conduction capability, and the heat generated by the hydrate cannot be effectively removed in time, so that the temperature of a gas hydration reaction system rises, and the gas hydration separation process is greatly weakened;

2. and (3) restriction of mass transfer: the gas and the water can not be fully contacted, and a plurality of multi-phase bodies form a plurality of phase interfaces, so that the mass transfer between gas phase and liquid phase in the system is seriously hindered, and the induction time is long and the hydrate generation rate is slow. The above problems result in long induction time, slow generation speed and large driving force of gas hydration reaction.

At present, the most mechanical strengthening method is to strengthen the generation of hydrate in a reaction kettle by stirring, the stirring mainly strengthens mass transfer and heat transfer, the liquid rotates along with blades, the gas-liquid contact area is increased, the gas dissolution efficiency is accelerated, and the heat generated by the generation of hydrate can be transferred in time. Further shortening the induction time of the hydrate, improving the generation rate, increasing the gas storage capacity and the like. The increase of stirring can increase the gas-liquid contact area, improve the gas hydration rate and ensure the fluid dispersibility. But the hydration reaction still stays at the gas-liquid interface, the induction time is not obviously shortened, and slight settlement and layering phenomena can be slightly generated in the kettle along with the increase of the experimental time, and the homogeneity is reduced although the particle suspension property can be met. In addition, the energy consumption of the system is increased by adding the blades for stirring, the system is not suitable for industrial production, and the danger of high-pressure gas leakage is increased by adding the stirring rotating shaft.

Therefore, in order to overcome the defects, a device for quickly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field needs to be provided.

Disclosure of Invention

Technical problem to be solved

The invention aims to solve the technical problem that the existing equipment has low gas hydration reaction efficiency.

(II) technical scheme

In order to solve the technical problems, the invention provides a device for quickly generating hydrates based on phase-change micro-nano fluid under the action of a magnetic field, which comprises an electric rotating table, a linear sliding table, clamping devices, magnetic steel, a high-pressure reaction kettle, a constant temperature box and an air compressor, wherein the linear sliding table is rotationally connected to the electric rotating table, a plurality of clamping devices are connected to the linear sliding table at intervals in a sliding manner, the magnetic steel is fixedly connected to the clamping devices, the high-pressure reaction kettle is placed between the clamping devices, and a target solution containing the phase-change micro-nano fluid is injected into the high-pressure reaction kettle; the electric rotating table, the linear sliding table, the clamp holder, the magnetic steel and the high-pressure reaction kettle are all placed in the constant temperature box, the air compressor is placed outside the constant temperature box, and the air compressor is connected with the high-pressure reaction kettle through a pipeline.

As a further explanation of the invention, preferably, the high-pressure reaction kettle is in a long cylinder shape, the material is titanium alloy which does not influence a magnetic field, and 1-3 temperature sensors and pressure sensors are inserted in the high-pressure reaction kettle.

As a further description of the present invention, preferably, the outer wall of the high-pressure reaction kettle is fixedly connected with a visible transparent window, and the visible transparent window is a transparent glass plate or a resin plate.

As a further explanation of the present invention, preferably, a threaded rod is rotatably connected to the linear sliding table, the threaded rod passes through a rotation axis of the linear sliding table, the two holders are respectively in threaded connection with two ends of the threaded rod, one end of the threaded rod extends out of the linear sliding table and is fixedly connected with a hand wheel, the hand wheel is connected with an industrial personal computer through an electrical lead, and the distance between the two holders is controlled by inputting a numerical value through the industrial personal computer.

As a further explanation of the invention, preferably, the motion distance range between the magnetic steels is 0-23 cm, and the magnetic field intensity range generated by the magnetic steels is 0-0.33T.

As a further explanation of the present invention, preferably, an input end of the air compressor is connected to an air cylinder through a pipeline, an output end of the air compressor is connected to an air storage tank through a pipeline, and the air storage tank is connected to the high-pressure reaction kettle through a pipeline.

As a further description of the present invention, it is preferable that a gas booster pump is further connected to a pipeline between the gas storage tank and the high pressure reaction vessel.

As a further description of the present invention, it is preferable that valves are mounted on a pipeline between the gas cylinder and the air compressor, a pipeline between the air compressor and the gas storage tank, and a pipeline between the gas booster pump and the high pressure reaction kettle, and the valves are electromagnetic valves.

As a further description of the present invention, it is preferable that an industrial personal computer, a data collector and a control motor are disposed outside the temperature control box, the data collector is electrically connected to the temperature sensor and the pressure sensor through electrical leads, the data collector is electrically connected to the industrial personal computer through electrical leads, the industrial personal computer is electrically connected to the control motor through electrical leads, the control motor is electrically connected to the electric rotating table through electrical leads, and the rotating speed of the magnetic field is controlled by inputting a numerical value to the control motor.

(III) advantageous effects

The technical scheme of the invention has the following advantages:

the phase-change micro-nano fluid replaces a single liquid phase, and the characteristics of high thermal conductivity and phase change heat absorption of the phase-change micro-nano particles are fully utilized, so that the multi-gas hydration reaction process is remarkably improved, and the gas hydration separation process is enhanced. The phase-change micro-nano particles have the characteristics of high specific surface area, active Brownian motion, small size, controllable concentration and the like, and can provide more active sites for the nucleation process of the hydrate. Therefore, the phase-change micro-nano fluid can well promote the heat transfer and mass transfer processes of gas hydration separation and strengthen the gas hydration separation process.

Drawings

FIG. 1 is a system diagram of a reaction apparatus of the present invention;

FIG. 2 is a sectional view of a reaction vessel according to the present invention.

In the figure: 1. an electric rotating table; 2. a linear sliding table; 21. a hand wheel; 3. a holder; 4. magnetic steel; 5. a high-pressure reaction kettle; 51. a temperature sensor; 52. a pressure sensor; 53. a visible transparent window; 6. a thermostat; 7. an air compressor; 71. a gas cylinder; 72. a gas storage tank; 73. a gas booster pump; 74. a valve; 8. an industrial personal computer; 81. a data acquisition unit; 82. and controlling the motor.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

A device for quickly generating hydrates based on phase-change micro-nano fluid under the action of a magnetic field, as shown in figure 1, comprises an electric rotating table 1, a linear sliding table 2, a clamper 3, magnetic steel 4 and a high-pressure reaction kettle 5, thermostated container 6, air compressor 7 and industrial computer 8, a word slip table 2 rotates to be connected on

electric rotating platform

1, 3 interval sliding connection of two holders are on a word slip table 2, magnet steel 4 links firmly on holder 3, high pressure reation kettle 5 places between holder 3, electric rotating platform 1, a word slip table 2, holder 3, magnet steel 4 and high pressure reation kettle 5 are all placed in thermostated container 6, air compressor 7 is placed outside thermostated container 6, air compressor 7 links to each other through the pipeline with high pressure reation kettle 5, industrial computer 8 also places outside thermostated container 6, industrial computer 8 and

electric rotating platform

1 and 5 electric connection of high pressure reation kettle.

As shown in fig. 1, the electric rotating table 1 is a rotating table with a rotating direction in a horizontal direction, the linear sliding table 2 is a circular rotating table, the bottom of the linear sliding table 2 is rotatably connected with the electric rotating table 1, the top of the linear sliding table 2 is rotatably connected with a threaded rod, the threaded rod passes through the rotating axis of the linear sliding table 2, the length direction of the threaded rod is horizontal, the two holders 3 are respectively in threaded connection with two ends of the threaded rod, and one end of the threaded rod extends out of the linear sliding table 2 and is fixedly connected with a hand wheel 21; by rotating the hand wheel 21, the two holders 3 can move towards the direction close to the high-pressure reaction kettle 5 or away from the high-pressure reaction kettle 5, so that the movement distance range between the magnetic steels 4 is 0-23 cm, and the magnetic field intensity range generated by the magnetic steels 4 is 0-0.33T.

With reference to fig. 1 and 2, the magnetic steel 4 is a square permanent magnet, the high-pressure reactor 5 is a long cylindrical structure made of titanium alloy material without affecting the magnetic field, the design pressure range is 0-10 MPa, and the design temperature is-10 ℃ to 50 ℃. The high-pressure reaction kettle 5 is filled with a target solution containing Ni-Mn-based phase-change micro-nano fluid. The Ni-Mn-based phase-change micro-nano particles are a shape memory material with thermoelastic martensite phase change, when the shape memory material is heated, the structure transformation from martensite to austenite, namely martensite reverse phase transformation, is generated, and the transformation of the crystal structure needs to provide external driving force, so that heat needs to be absorbed. 1-3 temperature sensors 51 and pressure sensors 52 are inserted into the high-pressure reaction kettle 5, the adopted temperature sensors 51 are four-base-point temperature sensors, the heat quantity of the hydrate at different positions in the generation process can be accurately quantified, and the four base points are respectively a gas phase point, a liquid surface point, a liquid middle point and a liquid bottom point; the 1-3 temperature sensors can quantify the heat of the wall of the reaction kettle, the center of the solution and the solution part; the outer wall of the high-pressure reaction kettle 5 is fixedly connected with a visible transparent window 53, the visible transparent window 53 is a high-pressure-resistant transparent glass plate or a high-pressure-resistant transparent resin plate, and the generation condition and the state of the hydrate in the high-pressure reaction kettle 5 can be observed at any time.

Referring to fig. 1 and 2, the incubator 6 includes a cooling system, a heating system, a control system, an air circulation system, a sensor system, and the like. The door body of the constant temperature box 6 is provided with a temperature control panel, and the constant temperature can be adjusted according to the experiment requirement. The temperature sensing probe is arranged in the 6 thermostated containers of thermostated container, can accurately master the inside temperature change of thermostated container and in time master the 6 inside temperatures of thermostated container and whether produce the discrepancy with the temperature of oneself settlement, can provide stable temperature environment for the experiment.

By adding Ni-Mn-based phase-change micro-nano fluid and a dispersing agent into a target solution, the phase-change micro-nano fluid replaces a single liquid phase, the characteristics of high thermal conductivity and phase change heat absorption of the phase-change micro-nano particles are fully utilized, so that the process of multi-gas hydration reaction is remarkably improved, the process of gas hydration separation is enhanced, more active sites can be provided for the nucleation process of hydrates, the heat in the hydration reaction can be absorbed, the problem that crystal nuclei are damaged by the heat generated in the nucleation process to cause the growth of a crystal structure to be slowed down is solved, meanwhile, based on the characteristic that the used material has magnetism, an external rotating magnetic field is combined, the particles are randomly browned and the micro-disturbance in the fluid is promoted, the energy transfer rate between the particles and the base solution is enhanced, the magnetic particles in the liquid are suspended in a high-pressure reaction kettle 5 through the magnetic field and rotate along with the magnetic, the phase-change micro-nano fluid can well promote the heat transfer and mass transfer processes of gas hydration separation and strengthen the gas hydration separation process.

Taking the example of using the NiMnGa phase-change micro-nano fluid, the induction time for generating the hydrate under 7.2MPa and 8.2MPa is only 11.3min and 3.17min, which is 94.21 percent and 98.37 percent shorter than the induction time (195.5min) of an SDS system; the consumed resources are less, the hydration reaction can be well promoted only by 0.1g of phase-change micro-nano particles, the phase-change micro-nano fluid can be reused and recycled, and the pollution to the environment is avoided.

As shown in fig. 1, an input end of the air compressor 7 is connected with an air bottle 71 through a pipeline, an output end of the air compressor 7 is connected with an air storage tank 72 through a pipeline, and the air storage tank 72 is connected with the high-pressure reaction kettle 5 through a pipeline. Wherein, the pipeline between the air bottle 71 and the air compressor 7, the pipeline between the air compressor 7 and the air storage tank 72, and the pipeline between the gas booster pump 73 and the high-pressure reaction kettle 5 are all provided with valves 74, and the valves 74 are electromagnetic valves. The air compressor 7 mainly functions to provide driving gas for the high-pressure reaction kettle 5, and the principle is as follows: after the air compressor unit in the air compressor 7 is connected with a 380V power supply, the operation is started, air in the air bottle 71 is sucked by the filter, the air is changed into compressed air through the reciprocating operation of the piston in the air cylinder, and the compressed air enters the air storage tank 72 through the air port pipeline and the one-way valve to be stored. The user opens valve 74 of gas holder 72 and can inject compressed air into high pressure batch autoclave 5 to the atmospheric pressure value of output compressed air is known to the accessible manometer, and the air compressor machine realizes opening through pressure switch and stops automatically. If the output pressure of the air compressor 7 does not reach the required pressure value, a gas booster pump 73 can be additionally arranged on the pipeline between the gas storage tank 72 and the high-pressure reaction kettle 5.

The gas booster pump 73 is a reciprocating, single-acting gas-driven pump. The gas booster pump 73 utilizes the large and small area difference of the two ends of the piston, low pressure acts on the large area end of the air pressure piston, and high pressure low flow gas is output at the small area end of the piston, so that the boosting effect is achieved. The output pressure of the gas booster pump 73 depends on the piston area ratio and the driving gas pressure and the pre-boost gas pressure. The area ratio of the piston of the equipment is 30: 1. the gas booster pump 73 is controlled by controlling the on-off of the driving gas through a solenoid valve. This equipment has been equipped with two accurate high pressure reducers, realizes the purpose of 5 pressures of accurate control high pressure batch autoclave through the knob of adjusting the pressure reducer. In order to prevent the backflow phenomenon of high-pressure gas, the equipment is also provided with a one-way valve on a pipeline.

As shown in fig. 1, an industrial personal computer 8, a data collector 81 and a control motor 82 are arranged outside the temperature control box 6, the industrial personal computer 8 is a common computer on the market, the data collector 81 is electrically connected with the temperature sensor 51 and the pressure sensor 52 through electrical leads, the data collector 81 is electrically connected with the industrial personal computer 8 through electrical leads, the industrial personal computer 8 is electrically connected with the control motor 82 through electrical leads, and the control motor 82 is electrically connected with the electric rotating platform 1 through electrical leads. The temperature sensor 51 and the pressure sensor 52 respectively transmit the measured data such as temperature values and pressure values in the gas hydration reaction process to a computer for collection, and display, record and store related data in real time. The computer adopts an industrial personal computer 8 with stable performance, and the safe implementation of the experimental test is ensured through the integral inspection and detection.

As shown in figure 1, when the hydration reaction of gas is needed, firstly, a specified amount of target solution is poured into a high-pressure reaction kettle 5, all systems and pipelines are connected, a linear sliding table 2 is adjusted to lead the distance between magnetic steels 4 to reach a specified distance, then the temperature of the system is adjusted to a preset temperature by using the constant temperature box 6, the valve 74 is opened, the gas in the gas cylinder 71 is filled into the high pressure reaction kettle 5 by using the air compressor 7 and the gas booster pump 73 to reach a preset pressure, then the valve 74 is closed, the opening and closing and the rotating speed of the electric rotating platform 1 are controlled by the rotating control motor 82, the measured temperature and pressure are transmitted to the data collector 81 through the temperature sensor 51 and the pressure sensor 52, and then the data are stored and processed by the industrial personal computer 8, during the gas hydration separation process, the state and the condition of the hydrate generation can be observed through the visible transparent window 53.

In conclusion, the phase-change micro-nano fluid fully utilizes the characteristics of high thermal conductivity and phase-change heat absorption of the phase-change micro-nano fluid, adopts the Ni-Mn-based phase-change micro-nano particles with martensite phase change, can absorb external heat when phase change occurs so as to reduce the environmental temperature, takes away heat generated in the hydrate generation process in time, and strengthens heat transfer in the gas hydration separation process. The micro-nano fluid has the characteristics of high specific surface area (the heat exchange area between particles and the fluid is increased, heat transfer is accelerated, more reaction interfaces are provided, the nucleation rate is improved), Brownian motion is active (the particles collide with each other at a gas-liquid boundary layer due to Brownian motion, the thickness of a mass transfer boundary layer is reduced, the mechanical property of surrounding liquid phase fluid can be changed), the size is small (when the size of the suspended particles is smaller than the thickness of the gas-liquid mass transfer boundary layer, the suspended particles can pass through the gas-liquid boundary layer to the gas-liquid interface to adsorb gas phase molecules and then return to a liquid phase main body under the action of osmosis so as to achieve the purpose of gas transportation), the concentration is controllable, and the like, and the gas hydration separation mass transfer process can be rapidly enhanced.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. Quick generation device of hydrate based on little nanometer fluid of phase transition type under the magnetic field effect, its characterized in that: the device comprises an electric rotating table (1), a linear sliding table (2), a holder (3), magnetic steel (4), a high-pressure reaction kettle (5), a thermostat (6) and an air compressor (7), wherein the linear sliding table (2) is rotationally connected to the electric rotating table (1), a plurality of holders (3) are connected to the linear sliding table (2) at intervals in a sliding manner, the magnetic steel (4) is fixedly connected to the holder (3), the high-pressure reaction kettle (5) is placed between the holders (3), and a target solution containing phase-change micro-nano fluid is injected into the high-pressure reaction kettle (5); electric rotating table (1), a straight sliding table (2), a holder (3), magnetic steel (4) and high-pressure reaction kettle (5) are all placed in a constant temperature box (6), an air compressor (7) is placed outside the constant temperature box (6), and the air compressor (7) is connected with the high-pressure reaction kettle (5) through a pipeline.

2. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 1, is characterized in that: the high-pressure reaction kettle (5) is in a long cylindrical shape, the material is titanium alloy which does not affect a magnetic field, and 1-3 temperature sensors (51) and pressure sensors (52) are inserted in the high-pressure reaction kettle (5).

3. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 2, is characterized in that: the outer wall of the high-pressure reaction kettle (5) is fixedly connected with a visible transparent window (53), and the visible transparent window (53) is a transparent glass plate or a resin plate.

4. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 1, is characterized in that: rotate on word slip table (2) and be connected with the threaded rod, the threaded rod passes word slip table (2) rotation axis, and two holder (3) threaded connection respectively are in the both ends of threaded rod, threaded rod one end is stretched out a word slip table (2) and is outer and linked firmly hand wheel (21), and hand wheel (21) are connected with the industrial computer through the electric lead, control the interval between two holder (3) through industrial computer input numerical value.

5. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 4, is characterized in that: the motion distance range between the magnetic steels (4) is 0-23 cm, and the magnetic field intensity range generated by the magnetic steels (4) is 0-0.33T.

6. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 1, is characterized in that: the input end of the air compressor (7) is connected with an air bottle (71) through a pipeline, the output end of the air compressor (7) is connected with an air storage tank (72) through a pipeline, and the air storage tank (72) is connected with the high-pressure reaction kettle (5) through a pipeline.

7. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 6, is characterized in that: a gas booster pump (73) is also connected on the pipeline between the gas storage tank (72) and the high-pressure reaction kettle (5).

8. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 7 is characterized in that: valves (74) are respectively arranged on a pipeline between the air bottle (71) and the air compressor (7), a pipeline between the air compressor (7) and the air storage tank (72), and a pipeline between the gas booster pump (73) and the high-pressure reaction kettle (5), and the valves (74) are electromagnetic valves.

9. The device for rapidly generating the hydrate based on the phase-change micro-nano fluid under the action of the magnetic field according to claim 2, is characterized in that: the temperature control box (6) is equipped with industrial computer (8) outward, data collection station (81) and control motor (82), data collection station (81) are through electric lead and temperature sensor (51) and pressure sensor (52) electric connection, data collection station (81) are through electric lead and industrial computer (8) electric connection, industrial computer (8) are through electric lead and control motor (82) electric connection, control motor (82) are through electric lead and electronic revolving stage (1) electric connection, come the rotatory rotational speed of control magnetic field through control motor input numerical value.