CN113842853A

CN113842853A - Magnetic control hydrate reaction generating device

Info

Publication number: CN113842853A
Application number: CN202111112002.6A
Authority: CN
Inventors: 王飞; 苑浩渝; 陈宸
Original assignee: Qingdao University of Science and Technology
Current assignee: Qingdao University of Science and Technology
Priority date: 2021-09-23
Filing date: 2021-09-23
Publication date: 2021-12-28

Abstract

The invention belongs to the technical field of gas hydrate preparation devices, and relates to a magnetron hydrate reaction generation device. The main structure includes a reaction kettle, a temperature sensor, a pressure sensor, a gas injection port, a water injection port, a coil module, a power amplifier, a signal generator and a Oscilloscope, the coil module wound outside the reactor generates a dynamically changing alternating magnetic field under the excitation of the modulated current, which drives the movement of the magnetic substances in the aqueous solution in the reactor. When rising, there is no problem of jamming of the motion mechanism and increased power consumption, and it has considerable industrial value in the fields of gas storage and transportation by hydrate method; it uses the alternating magnetic field generated by the external coil module of the reactor and the internal The interaction between micro- and nano-magnons is the core and starting point, and the non-contact magnetic drive is applied to the stirring of hydrate reaction aqueous solution, especially for the stirring of water in the hydrate gap when the solid content is high in the later stage of the reaction.

Description

Magnetic control hydrate reaction generating device

The technical field is as follows:

the invention belongs to the technical field of gas hydrate preparation devices, and relates to a magnetic control hydrate reaction generation device which can stir liquid to realize rapid generation of gas hydrate without adopting a moving part.

Background art:

the gas hydrate is a cage-shaped structure formed by water and small molecule gas, the water forms a water molecular grid through hydrogen bonds, the gas molecules are limited in the water molecular grid and support the water molecular grid, and the gas molecules mainly comprise methane, ethane, propane, carbon dioxide, hydrogen and the like. Theoretically, a gas hydrate of a unit volume can store about 170 times of gas molecules, and can be stored for a long time at low temperature and normal pressure with only trace decomposition, and the decomposition is mild without risks such as leakage explosion and the like. Based on this, gas hydrates have been widely studied for the field of storage and transportation of gases, but are limited by the slow rate of formation of gas hydrates.

The generation of the gas hydrate belongs to gas-liquid-solid three-phase reaction, namely, gas molecules and water generate solid hydrate, in the reaction process, the gas molecules and water molecules generate a layer of hydrate film at an interface, and the gas molecules cannot penetrate through the hydrate film to be effectively contacted with the water molecules in the liquid phase for further reaction. Currently, methods for increasing the rate of hydrate reaction generally include both physical and chemical methods: physical methods mainly include stirring, spraying, bubbling, jetting, and the like, which provide a constantly renewed gas-liquid contact area mainly by breaking the hydrate film; the chemical method is mainly to add chemical substances for reducing the surface tension of the gas-liquid interface, such as a surfactant and amino acid, so that gas molecules pass through the gas-liquid interface under the condition of low resistance.

The main structure of a continuous reaction device for hydrates by utilizing concentric double-spiral type disclosed in Chinese patent 202010993801.8 comprises an outer reaction kettle, a central reaction kettle and a motor; a central reaction kettle is sleeved in the outer reaction kettle and driven by a motor; the main structure of the outer reaction kettle comprises an outer cylinder body, an outer stirring blade, a pressure sensor, a temperature sensor, a discharge hole and a ball valve; an outer stirring blade is arranged in the outer cylinder, a pressure sensor and a temperature sensor are arranged at the upper part of the outer cylinder, a discharge hole is formed in the lower part of the outer cylinder, and a ball valve is arranged at the discharge hole; the main structure of the central reaction kettle comprises a central cylinder, a stirring rod, a central stirring blade, a through hole, a liquid spraying port and an air inlet; a stirring rod is arranged in the center of the interior of the central cylinder, a central stirring blade is arranged on the stirring rod, a plurality of through holes are uniformly formed in one end of the central cylinder, and a liquid spraying port and an air inlet are formed in the other end of the central cylinder; the through hole is a passage for hydrate particles to enter the outer reaction kettle from the central reaction kettle, and the hydrate particles are conveyed to the discharge hole by the outer stirring blade and discharged; the liquid spraying port is used for spraying micro liquid drops; the gas inlet is used for injecting gas.

The natural gas hydrate synthesis reaction kettle disclosed in the chinese patent 201920848186.4 is further provided with a pressure gauge, a thermometer, a gas inlet, a gas outlet and a liquid inlet, the reaction kettle comprises a reaction chamber and a storage chamber, the upper part of the reaction chamber is provided with a connection port a, the upper part of the storage chamber is provided with a connection port B, the connection port a is higher than the connection port B, and the connection port a and the connection port B are communicated through a pipeline; this reation kettle still is provided with liquid circulation injection system, liquid circulation injection system is including the circulating pump, heat exchanger and the sprayer that connect gradually, the entry and the apotheca bottom intercommunication of circulating pump, the sprayer is located the inside upper end of reacting chamber, the export and the sprayer top intercommunication of heat exchanger, the side of sprayer is provided with the sprayer air inlet, sprayer air inlet position is higher than connector A, the export of sprayer is located the reacting chamber lower part.

The main structure of a spray type hydrate continuous reaction device disclosed in Chinese patent 202110339614.2 comprises a reaction kettle, a fluidization restrictor shell and a pipeline; the bottom of the reaction kettle is connected with a fluidization flow controller, the periphery of the fluidization flow controller is provided with a fluidization flow controller shell, the bottom of the fluidization flow controller is connected with a pipeline, the reaction kettle is formed by sequentially connecting a cover body, an upper cylinder and an upper cone, the upper part of the upper cylinder is provided with an air inlet pipe and a liquid inlet pipe, the periphery of the upper cylinder is provided with a cooling jacket, the bottom of the upper cone is provided with a flange, the fluidization flow controller is formed by sequentially connecting an upper porous cone, a throttling cylinder and a lower porous cone, the top of the upper porous cone is provided with an upper flange, the bottom of the lower porous cone is provided with a lower flange, a plurality of air holes are arranged on the upper porous cone and the lower porous cone at equal intervals, the fluidization flow controller shell is formed by sequentially connecting a transition cylinder, a lower cone and a lower cylinder from top to bottom, the top of the transition cylinder is provided with a flange II, the bottom of lower cylinder is provided with the flange No. three, and the top of pipeline is provided with the flange No. four.

Although the prior art and the above patents relate to apparatuses and methods capable of effectively increasing the contact area of gas and liquid and increasing the hydrate reaction rate, with the formation of hydrate and the increase of solid content, the moving structures in the apparatus, such as: the stirring paddle and related parts such as holes, pipe orifices and the like in the spraying, bubbling, jetting and other systems face the problems of shell blocking and blockage, so that the equipment cannot effectively provide a gas-liquid contact surface required by hydrate reaction, the energy consumption is increased rapidly, even the stable operation of the equipment is influenced, and potential safety hazards are brought. Meanwhile, the hydrate generation reaction belongs to a high-pressure reaction, and the adoption of a dynamic structure in the reaction kettle can also put high requirements on the sealing of equipment. Therefore, in order to realize the rapid generation of hydrate and improve the safety and simplicity of reaction equipment, novel hydrate reaction equipment needs to be developed.

The invention content is as follows:

the invention aims to overcome the defects in the prior art, and seeks to design a high-efficiency magnetic control hydrate reaction generation device so as to realize the stirring effect without a clamping shell in the whole process of the hydrate reaction under the static sealing condition, simplify the structure of the hydrate reaction device and improve the usability, safety and operability.

In order to achieve the purpose, the main structure of the magnetic control hydrate reaction generation device comprises a reaction kettle, a temperature sensor, a pressure sensor, a gas injection port, a water injection port, a coil module, a power amplifier, a signal generator and an oscilloscope; the end part of the reaction kettle is provided with a temperature sensor, a pressure sensor, a gas injection port and a water injection port, the outer side of the reaction kettle is provided with a coil module, the coil module is connected with a signal generator through a power amplifier, and the power amplifier is connected with an oscilloscope.

The reaction kettle related by the invention is a high-pressure reaction kettle; the coil module comprises three groups of six coils, the current of the same group of coils flows in the same phase and in the opposite direction, the coil distance is half or one time of the diameter of the coil, the frequency is 1-50HZ, the coil module is made of glass-covered wires and enameled wires, and the coil module is circular, square, saddle-shaped and tile-shaped; the signal generator provides a sinusoidal, pulsed or square wave alternating current to the coil module.

When the magnetic control hydrate reaction generation device related by the invention is used, as shown in figure 1, a reaction kettle, a temperature sensor, a pressure sensor, a gas injection port, a water injection port and a coil module are firstly arranged in a constant temperature box, then the temperature sensor and the pressure sensor are electrically connected with a computer through a data collector, the gas injection port is connected with a high-pressure gas steel cylinder, the water injection port is connected with a magnetic fluid storage tank through a constant flow pump, and magnetic fluid is injected into the magnetic fluid storage tank; setting the temperature value of a constant temperature box to be 1 ℃, starting cooling, opening a high-pressure gas steel cylinder when a temperature sensor monitors that the temperature of a reaction kettle is 1 ℃, closing the high-pressure gas steel cylinder when a pressure sensor monitors that the pressure of the reaction kettle is 6MPa, modulating current signal modes, frequencies, phases and assignments of different channels in a signal generator according to requirements, amplifying current signals generated by the signal generator by a power amplifier and then introducing the amplified current signals into a coil module, simultaneously, starting an oscilloscope to display and record the current signal modes and intensity values output by the power amplifier, allowing magnetic fluid to enter the reaction kettle through a water injection port, forming an alternating magnetic field space by the coil modules with different specifications and shapes on the periphery of the reaction kettle after introducing low-frequency alternating current, and generating a variable magnetic field in the constant temperature box after the alternating magnetic field space passes through the reaction kettle without generating eddy current on the inner wall of the reaction kettle to cause heat and inhibit the generation of hydrates, hydrates capable of generating methane, hydrogen, carbon dioxide and argon; in the process, the data collector collects temperature and pressure data in the reaction kettle in real time through the temperature sensor and the pressure sensor.

Magnetons with high stability and high magnetic content and with nano and micron dimensions are distributed in the magnetofluid, and the magnetons are called micro-nano magnetons for short; the micro-nano magnetons comprise magnetic micro-nano magnetons synthesized by a ferron coprecipitation method on a substrate of a high-molecular nanosphere, a carbon nano tube, graphene, activated carbon, seaweed or hydrogel, and core-shell structure micro-nano magnetons which are prepared by a chemical modification method (oleic acid coating, CTAB coating, tetraethyl silicate coating, dopamine coating and silicon dioxide coating) and can improve stability by taking ferroferric oxide, magnetic ferrite or alloy materials as cores; the micro-nano magnetons rotate under the action of the alternating magnetic field so as to realize micro-convection stirring effect on the local part of the aqueous solution, so that the magnetons distributed in each water phase realize the micro-convection stirring effect of nano and micron scales on each part of the water phase, and efficient gas-liquid mass transfer is realized.

Compared with the prior art, the coil module wound outside the reaction kettle generates a dynamically-changing alternating magnetic field under the excitation of the modulated current to drive the movement of magnetic substances in aqueous solution in the reaction kettle, so that the stirring effect on the aqueous solution is realized, the generation of hydrate is promoted, no moving mechanism is arranged in the reaction kettle, the problems of shell clamping and power consumption increase of the moving mechanism are solved when the solid content is increased in the later stage of hydrate reaction, and the method has considerable industrial value in the fields of hydrate method gas storage, transportation and the like; the interaction between an alternating magnetic field generated by a coil module outside the reaction kettle and micro-nano magnetons in the reaction kettle is used as a core and a starting point, non-contact magnetic drive is applied to stirring of a hydrate reaction aqueous solution, particularly the stirring of water in a hydrate gap when the reaction later stage is performed with a prominent effect on high solid content is performed, so that the hydrate generation equipment is simple in structure, safe, reliable, simple and easy to operate and convenient to maintain.

Description of the drawings:

fig. 1 is a schematic view of the main structure and the operation state thereof.

Fig. 2 is a layout diagram of a coil according to embodiment 1 of the present invention.

Fig. 3 is a layout diagram of a coil according to embodiment 2 of the present invention.

Fig. 4 is a layout diagram of a coil according to embodiment 3 of the present invention.

FIG. 5 is a transmission electron micrograph (500000X magnification) of a magnetic fluid according to the present invention.

FIG. 6 is a transmission electron micrograph (400000 Xmagnification) of a magnetic fluid according to the present invention.

Fig. 7 is a macroscopic image of the magnetic fluid according to the present invention.

The specific implementation mode is as follows:

the invention is further described below by way of an embodiment example in conjunction with the accompanying drawings.

Example 1:

the main structure of the magnetic control hydrate reaction generation device related to the embodiment comprises a reaction kettle 1, a temperature sensor 2, a pressure sensor 3, an air injection port 4, a water injection port 5, a coil module 6, a power amplifier 7, a signal generator 8 and an oscilloscope 9; the end part of the reaction kettle 1 is provided with a temperature sensor 2, a pressure sensor 3, an air injection port 4 and a water injection port 5, the outer side of the reaction kettle is provided with a coil module 6, the coil module 6 is connected with a signal generator 8 through a power amplifier 7, and the power amplifier 7 is connected with an oscilloscope 9; the coil module 6 comprises three groups of six coils which are respectively positioned above, below, leftward, rightward, forward and backward of the reaction kettle 1 and are all circular, the distances between the coils above and below, between the coils leftward and rightward and between the coils forward and backward are half of the diameter of the coils, the current directions are the same, and the phase difference is 90 degrees, as shown in fig. 2.

When the magnetic control hydrate reaction generation device is used, a reaction kettle 1, a temperature sensor 2, a pressure sensor 3, an air injection port 4, a water injection port 5 and a coil module 6 are placed in a constant temperature box 11, the temperature sensor 2 and the pressure sensor 3 are electrically connected with a computer 13 through a data collector 12, the air injection port 4 is connected with a high-pressure gas steel cylinder 14, the water injection port 5 is connected with a magnetic fluid storage tank 16 through a constant flow pump 15, and magnetic fluid is injected into the magnetic fluid storage tank 16; setting the temperature value of a thermostat 11 as 1 ℃, starting cooling, opening a high-pressure gas steel cylinder 14 when a temperature sensor 2 monitors that the temperature of a reaction kettle 1 is 1 ℃, closing the high-pressure gas steel cylinder 14 when a pressure sensor 3 monitors that the pressure of the reaction kettle 1 is 6MPa, modulating current signal modes, frequencies, phases and assignments of different channels in a signal generator 8 according to requirements, amplifying current signals generated by the signal generator 8 through a power amplifier 7 and then introducing the amplified current signals into a coil module 6, simultaneously, starting an oscilloscope 9 to display and record the current signal modes and intensity values output by the power amplifier 7, enabling magnetic fluid to enter the reaction kettle 1 through a water injection port 5, forming an alternating magnetic field space after introducing low-frequency alternating current into the coil module 6 with different specifications and shapes on the periphery of the reaction kettle 1, and generating a changing magnetic field in the thermostat 11 after the alternating magnetic field space with low-frequency changes through the reaction kettle 1, but does not generate vortex on the inner wall of the reaction kettle 1 to generate heat to inhibit the generation of hydrate, and can generate hydrate of methane, hydrogen, carbon dioxide and argon; in the process, the data collector 12 collects the temperature and pressure data in the reaction kettle 1 in real time through the temperature sensor 2 and the pressure sensor 3.

The magnetofluid related to the embodiment is prepared by taking ferroferric oxide as a core and performing surface chemical modification by using oleic acid, transmission electron micrographs are shown in fig. 5 and 6, wherein the ferroferric oxide is in a central area, the oleic acid is in a surrounding light-colored area, and a macroscopic physical image is shown in fig. 7.

The magnetic control hydrate reaction generation device related to the embodiment utilizes the rotation effect of micron and nanometer scale magnetons in an alternating magnetic field space to realize the stirring effect on each part of a water phase space, increases the contact area between gas and liquid, and improves the turbulence degree in an aqueous solution system, and especially in the later stage of the generation and generation of hydrates, the micron and nanometer scale magnetons are small in scale, so that the unreacted aqueous solution in the hydrate gaps can be stirred slightly, which cannot be realized by other technologies such as macroscopic stirring; secondly, because the alternating magnetic field penetrates through the stirring effect of the reaction kettle 1 on the micro-nano magnetons of the internal aqueous solution, the interior of the reaction kettle 1 is not provided with a movement mechanism, and only interfaces of the temperature sensor 2 and the pressure sensor 3, the gas injection port 4 and the water injection port 5 are needed to be arranged, so that the structure of the hydrate high-pressure reaction kettle in the prior art is greatly simplified, the problem of shell clamping of the movement mechanism is completely eliminated, and the stable and continuous operation of hydrate reaction is ensured.

Example 2:

the main structure of the magnetron hydrate reaction generating device according to this embodiment is the same as that of embodiment 1, except that the coils located at the left, right, front and rear of the reaction vessel 1 are square, as shown in fig. 3.

Example 3:

the main structure of the magnetron hydrate reaction generating device according to this embodiment is the same as that of embodiment 1, except that the coils located at the left, right, front and rear of the reaction vessel 1 are all in a tile shape, as shown in fig. 4.

Claims

1. a magnetron hydrate reaction generating device, characterized in that the main structure comprises a reactor, a temperature sensor, a pressure sensor, a gas injection port, a water injection port, a coil module, a power amplifier, a signal generator and an oscilloscope; A temperature sensor, a pressure sensor, a gas injection port and a water injection port are arranged on the outside of the reactor, and a coil module is arranged on the outside of the reaction kettle. The coil module is connected with the signal generator through a power amplifier, and the power amplifier is connected with an oscilloscope.

2 . The magnetron hydrate reaction generating device according to claim 1 , wherein the reactor is a high-pressure reactor. 3 .

3. The magnetron hydrate reaction generating device according to claim 2, wherein the coil module comprises three groups of six coils, the currents of the coils in the same group are in the same phase and flow in opposite directions, and the coil distance is half the coil diameter or Double, the frequency is 1-50HZ, the material includes glass-coated wire and enameled wire, and the shape includes round, square, saddle and tile.

4 . The magnetron hydrate reaction generating device according to claim 3 , wherein the signal generator provides a sinusoidal, pulsed or square-wave alternating current for the coil module. 5 .

5. The magnetron hydrate reaction generating device according to claim 4, characterized in that, when in use, the reactor, temperature sensor, pressure sensor, gas injection port, water injection port and coil module are first placed in a constant temperature box, and then The temperature sensor and the pressure sensor are electrically connected to the computer through the data collector, the gas injection port is connected to the high-pressure gas cylinder, the water injection port is connected to the magnetic fluid storage tank through the constant current pump, and the magnetic fluid is injected into the magnetic fluid storage tank; The temperature value of the reactor is set to 1 °C, and the temperature is lowered. When the temperature sensor detects that the temperature of the reactor is 1 °C, open the high-pressure gas cylinder. When the pressure sensor detects that the pressure of the reactor is 6MPa, close the high-pressure gas cylinder and follow the requirements. Modulate the current signal mode, frequency, phase and assignment of different channels in the signal generator. The current signal generated by the signal generator is amplified by the power amplifier and then passed to the coil module. At the same time, the oscilloscope is turned on to display and record the current signal mode output by the power amplifier. and the intensity value, the magnetic fluid enters the reactor through the water injection port to generate hydrates of methane, hydrogen, carbon dioxide and argon.

6 . The magnetron hydrate reaction generating device according to claim 5 , wherein the coil modules of different specifications and shapes around the reactor form an alternating magnetic field space after passing in a low-frequency alternating current, and the alternating magnetic field space that changes at a low frequency. 7 . After passing through the reaction kettle, a changing magnetic field is generated inside the constant temperature box, and eddy currents are not generated on the inner wall of the reaction kettle to cause heat to inhibit the formation of hydrates.

7. The magnetron hydrate reaction generating device according to claim 5 or 6, characterized in that, during use, the data collector collects the temperature and pressure data in the reaction kettle in real time through a temperature sensor and a pressure sensor.

8 . The magnetron hydrate reaction generating device according to claim 5 , wherein the magnetic fluid contains magnetons with high stability and high magnetic content in nanometer and micrometer scales, referred to as micro-nano magnons for short. 9 .

9 . The magnetron hydrate reaction generating device according to claim 8 , wherein the micro-nano magnetons are included on a substrate made of polymer nanospheres, carbon nanotubes, graphene, activated carbon, seaweed or hydrogel. 10 . The magnetic micro-nano magnons synthesized by the ferrite co-precipitation method use ferric tetroxide, magnetic ferrite or alloy materials as the core, and the core-shell structure micro-nano magnons are prepared by chemical modification method, which can improve the stability.

10. The magnetron hydrate reaction generating device according to claim 5, 8 or 9, wherein the micro-nano magnetons rotate under the action of an alternating magnetic field to locally achieve a micro-convective stirring effect on the aqueous solution, so that they are distributed in each The magnetons in the water phase can achieve nano- and micro-scale micro-convective stirring for various parts of the water phase.