Circulating water type plasma magnetically stabilized fluidized bed conversion device and method for treating co2 to produce liquid fuel

Abstract

The present application relates to a circulating water type plasma magnetically stabilized fluidized bed conversion device and a method for preparing liquid fuel by processing CO2, the device comprising a power / gas supply unit, a plasma fluidized bed unit, a magnetic control unit and a fuel collection unit; a mixed gas containing CO2 raw material is introduced into a magnetically stabilized fluidized bed reactor, a magnetic hydrophobic catalyst is stably suspended in the central region of the reactor under the dual action of gas flow and magnetic field, and is further coupled with a non-equilibrium plasma, so that high-flux CO2 gas can be rapidly converted into high-value liquid chemicals such as methanol and acetic acid under mild conditions; the magnetically stabilized fluidized bed can be powered by clean electricity, a circulating water system is arranged outside the reactor, the reaction temperature, discharge power and magnetic field strength can be independently adjusted, which is beneficial to the regulation of the conversion process and realizes the maximum synergy between the plasma and the magnetic hydrophobic catalyst; the device can be expanded for other plasma technology dominated energy conversion processes, and the one-step high-value utilization of target small molecules under mild conditions is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a CO2 magnetic control conversion device and method under mild conditions, in particular to a circulating water type plasma magnetically stabilized fluidized bed conversion device and a method for processing CO2 to prepare liquid fuel, which can convert raw materials such as CO2, H2 and CH4 into high value-added liquid chemicals under the synergistic catalysis of plasma and catalyst. BACKGROUND

[0002] The plasma-catalyst synergistic CO2 conversion effect is closely related to the discharge form, discharge intensity, reaction temperature, catalyst and reactor type. In particular, strengthening the interaction between active particles and the surface of the catalyst can effectively regulate the reaction selectivity and improve the synergistic conversion rate (Fuel Processing Technology, 2023, 242, 107648). However, most current plasma-catalyst synergistic CO2 conversion processes are concentrated in fixed-bed DBD reactors. In order to reduce the reaction pressure drop, the solid catalyst needs to be granulated and filled in the discharge area, which results in only a limited number of surface active sites participating in the conversion, poor heat and mass transfer effect, and the synergistic effect still needs to be improved. The gas-solid fluidized bed reactor has the advantages of large gas-solid two-phase contact area and sufficient mixing, which can make the raw gas and catalyst particles fully contact and produce convection, thereby simultaneously realizing efficient mass transfer, heat transfer and chemical reaction process. Batiot-Dupeyrat (Fuel, 2021, 288, 119575) compared the differences in reactor types in plasma catalysis, and found that the specific surface area of Al2O3 pellets increased from 260 m 2 / g to 312 m 2 / g, the CH4 conversion rate in the fluidized bed increased by 42%, and the CO2 conversion rate increased by nearly 1 times, while the trend in the fixed bed reactor was opposite, which was due to the fact that in the fluidized bed, the entire particle surface participated in the catalytic process, maximizing the synergistic effect of plasma and catalyst, while in the fixed bed, the limited active sites were mainly concentrated in the particle contact point position, and a distorted electric field was formed, which limited the synergistic catalytic effect.

[0003] A fluidized bed type DBD plasma organic matter contaminated soil remediation system is disclosed in Chinese Invention Patent No. 202022657310.4, granted on September 28, 2021. The main feature is that the fluidized bed cavity is a barrel-shaped container with a stainless steel barrel wall. The DBD reaction tube is composed of a high-voltage electrode, an insulating medium, and a low-voltage electrode arranged coaxially. The high-voltage electrode is arranged inside the insulating medium, and the low-voltage electrode is uniformly distributed in a hexagonal shape around the insulating medium. The insulating medium is made of ceramic medium. After the gas passes through the stainless steel filter screen, the soil is blown into a fluidized state. The fluidized soil moves up and down in the DBD reaction tube for treatment, solving the problems of low efficiency and secondary pollution in existing remediation processes.

[0004] The above invention solves the problem of effective contact between raw gas and solid material to some extent. However, due to the gravitational field and the viscosity of the catalyst itself, similar to traditional fluidized beds, the existing plasma fluidized bed reactor also faces the following problems: (1) Different particle sizes lead to uneven residence time in the reactor and agglomeration between particles after adsorption of H2O; (2) The relative speed of gas-solid two-phase is out of sync, and the strong electrostatic effect causes the catalyst powder to accumulate on the surface of the inner high-voltage electrode; (3) According to thermodynamic equilibrium, low temperature is beneficial for the conversion of CO2 to produce high-value liquid chemicals (such as CH3OH, CH3COOH), and high temperature is beneficial for the balance to move towards gas products (such as CO). The temperature rise effect in plasma conversion has not been effectively addressed.

[0005] Chinese Invention Patent No. 201310040878.3, granted on September 17, 2014, discloses a method for preparing chlorine gas by hydrogen chloride oxidation using a magnetic stable fluidized bed. The main feature is that the gas stream containing molecular oxygen and the gas stream containing hydrogen chloride are thoroughly mixed, and the mixed gas is preheated and sent into the magnetic stable fluidized bed reactor, where the oxygen chlorination reaction occurs under the action of the magnetic catalyst to produce chlorine gas, and the heat released during the reaction is removed to produce steam. The magnetic stable fluidized bed reactor is externally provided with a stable magnetic field in the axial and radial directions, and the magnetic fields in the two directions are alternately operated with time. This method can effectively enhance the mass transfer and heat transfer effect of two-phase catalytic reaction, improve the reaction equilibrium conversion rate, increase the stable operation time of the device, and reduce the energy consumption in the production process.

[0006] It can be seen that the use of an external magnetic field can effectively improve the shortcomings of traditional fluidized bed poly-state fluidization mass transfer. However, it is not appropriate to simply combine the above existing inventions into a magnetic stable plasma fluidized bed reaction device, and the main reasons are as follows: (1) The external magnetic field will deflect the charged particles in the plasma channel, changing the discharge state and position; (2) At the same time, a strong magnetic field will cause magnetic particles to agglomerate towards the wall, making fluidization difficult.

[0007] Therefore, it is urgent to improve the internal structure of the existing plasma fluidized bed, on the one hand, to design a magnetic hydrophobic catalytic material for the plasma fluidized bed, and on the other hand, to realize the stable suspension and fluidization of solid particles through the double regulation of flow field action and electromagnetic field Lorentz force, and finally to introduce circulating water cooling to reduce the reaction temperature and improve the selectivity of fuel.

[0008] The current plasma fluidized bed CO2 reactor still follows the traditional hot catalytic fluidized bed design idea, and lacks effective stable fluidization technology and temperature control. The strong static electricity causes the gradual pulverization of the catalyst and the accumulation on the surface of the electrode, and the generated products are mainly CO, C x H y The selectivity of high value-added liquid chemicals is improved. SUMMARY

[0009] The application provides a circulating water type plasma magnetic stable fluidized bed conversion device and a method for preparing liquid fuel by treating CO2. The device and method are a fluidized bed conversion device capable of continuously generating plasma and a method for efficiently preparing liquid fuel by treating CO2. The device comprises a power / gas supply unit, a plasma fluidized bed unit, a magnetic control unit and a liquid fuel collection unit. A mixed gas containing CO2 raw material is introduced into the magnetic stable fluidized bed reactor. The magnetic hydrophobic catalyst is stably suspended in the central region of the reactor under the double action of the flow field and the magnetic field, and is further coupled with the non-equilibrium plasma. High flux CO2 gas and other gases can be rapidly converted into high value liquid chemicals under mild conditions. The magnetic stable fluidized bed can be powered by clean electricity. A circulating water system is arranged outside the reactor. The reactor temperature, plasma discharge and magnetic field strength can be independently adjusted, which effectively avoids the interference of the magnetic field on the plasma, facilitates the conversion process control, and realizes the maximum synergy between the plasma and the magnetic catalyst. The device can be expanded for other energy conversion processes dominated by plasma technology, and the one-step high value utilization of target small molecules under mild conditions is improved.

[0010] The technical scheme of the application is as follows:

[0011] A circulating water type plasma magnetic stable fluidized bed conversion device comprises a solar cell panel, a controller, an energy storage battery, an inverter, a plasma power supply, a ball valve, a gas mixing tank, a hollow metal electrode, an insulating sleeve, a gas outlet, a reactor cavity, a permanent magnet, a direct current driving power supply, a movable support, a circulating water interlayer, a magnetic hydrophobic catalyst, a circulating water machine, a sliding resistor, an electromagnetic coil, a tail blow joint, a coaxial buckle, a gas-liquid separator, a condensation tank, a gas collection and utilization device and a liquid collection and utilization device.

[0012] The solar cell panel is sequentially connected with the controller, the energy storage battery and the inverter. The first output end of the inverter is sequentially connected with the plasma power supply and the hollow metal electrode.

[0013] The second output end of the inverter is connected with a DC driving power supply, a sliding resistor and an electromagnetic coil in sequence; and the gas mixing tank is connected with a ball valve and a hollow metal electrode in sequence.

[0014] The top of the reactor cavity is covered with an insulating sleeve; the upper part of the reactor cavity is provided with a gas outlet; the gas outlet is connected with a gas-liquid separator; the gas-liquid separator is placed in a condensation tank; the top of the gas-liquid separator is connected with a gas collection and utilization device; and the lower part of the gas-liquid separator is connected with a liquid collection and utilization device.

[0015] The hollow metal electrode penetrates through the insulating sleeve and extends into the reactor cavity; the outer periphery of the reactor cavity is provided with a circulating water jacket; the top water outlet of the circulating water jacket is connected with the upper water inlet of a circulating water machine; the lower water outlet of the circulating water machine is connected with the water inlet of the circulating water jacket; the lower part of the reactor cavity is provided with a coaxial buckle which fixes the tail part of the hollow metal electrode; and the bottom of the hollow metal electrode is provided with a tail blow joint.

[0016] The outer upper end of the reactor cavity is sequentially sleeved with a permanent magnet and an electromagnetic coil from inside to outside; the outer lower end of the insulating sleeve is sequentially sleeved with a permanent magnet and an electromagnetic coil from inside to outside; the permanent magnet at the outer upper end of the insulating sleeve and the permanent magnet at the outer lower end of the insulating sleeve are fixedly connected through a movable support; and a magnetic hydrophobic catalyst is arranged in the middle part of the reactor cavity.

[0017] The fluidized bed conversion device capable of continuously generating plasma is characterized in that specific magnetic solid particles are stably suspended and fluidized through the double regulation of the reactor bottom flow field and the parallel Lorentz force of the electromagnetic field, without introducing a radial magnetic field; the reactor temperature, plasma discharge and magnetic field strength can be independently adjusted, effectively avoiding the interference of the magnetic field on the plasma; and the introduction of circulating water cooling reduces the reaction temperature and improves the fuel selectivity. The device comprises a power supply / gas supply unit, a plasma fluidized bed unit, a magnetic control unit and a fuel collection unit.

[0018] The power supply unit can utilize commercial power or clean power, preferably clean power, including a solar panel, a controller, an energy storage battery and an inverter; and the gas supply part includes a gas mixing tank, a ball valve and an insulating pipeline a.

[0019] The plasma fluidized bed unit includes a plasma power supply, a high-voltage input line, a reactor cavity, an insulating sleeve, a magnetic hydrophobic catalyst, a hollow metal electrode, a coaxial buckle, a tail blow joint, a circulating water machine, a circulating water pipeline and a circulating water jacket.

[0020] The magnetic control unit includes a DC driving power supply, a sliding resistor, a permanent magnet, an electromagnetic coil and a movable support.

[0021] The fuel collection unit comprises an insulating pipeline b, a gas-liquid separator, a condensation tank, a gas collection and utilization device and a liquid collection and utilization device;

[0022] The solar panel is used for converting solar energy into direct current, and the output voltage is generally between 18-36V, and the output power is set according to the use requirement;

[0023] The controller is adapted to the current generally between 10-60A, and is used for displaying the charging state of the solar panel and protecting the energy storage device from overcharging;

[0024] The energy storage battery is used for storing the electric energy converted by the solar panel, the input and output voltage of the battery is generally set to 12V, and the capacity is adapted according to the power of the solar panel;

[0025] The inverter is used for inverting the direct current output by the energy storage device into 220V alternating current, and the power is generally between 1000-6000W;

[0026] The plasma power supply is used for exciting the uniform discharge plasma generated in the fluidized bed, and the power supply is not limited to a high-frequency alternating current source, a direct current source, a pulse source, a radio frequency source and the like, and the specific setting parameters are set according to the requirement;

[0027] The reactor cavity, the insulating sleeve and the coaxial buckle are not limited to glass, quartz, alumina and polytetrafluoroethylene, the reactor cavity is preferably quartz, and the insulating sleeve and the coaxial buckle are preferably polytetrafluoroethylene;

[0028] The high-voltage input line has a voltage resistance requirement of not less than 15kV;

[0029] The hollow metal electrode serves as a high-voltage input end and an air inlet end, and can be made of conductive metal materials such as aluminum, iron, copper and stainless steel;

[0030] The magnetic hydrophobic catalyst comprises a magnetic catalyst loaded on a non-magnetic carrier, which is prepared by using a hydrotalcite precursor method (MMgAl-LDH, M=Fe, Co, Ni) and supplemented by a calcination reduction process, the magnetic component is Fe, Co or Ni alone or a combination of several components, the non-magnetic carrier is a mixed oxide of MgO-Al2O3, the mass ratio of the prepared magnetic catalyst and polytetrafluoroethylene is between 0.5-2, the mass fraction of the magnetic component is preferably 30%-50%, the size of the loaded magnetic particles is preferably 5-20nm, and the size of the catalyst granulation is preferably 80-100 mesh;

[0031] The tail blow joint outlet aperture is preferably between 1-2mm, the initial state fluidization of the particles is realized through a bottom high-flow field, and the fluidization air speed is preferably between 1L / min / g-3L / min / g;

[0032] The circulating water pipeline is preferably made of polyurethane, polyether, etc. and is used for gas supply or liquid circulation.

[0033] The circulating water sandwich comprises a water inlet and a water outlet, and forms a circulating water circuit with the circulating water unit. The water flows from the bottom to the top. The water temperature is preferably set to 5-60℃.

[0034] The direct current driving power supply has a voltage range of 0-60V, a current of 0-20A, and a power range that can be adjusted.

[0035] The permanent magnet material is not limited to RbFeB, SmCo, ferrite, etc. and is preferably a ferrite material, which is used to enhance the strength of the applied magnetic field.

[0036] The electromagnetic coil is preferably a copper coil. The number of turns and the wire diameter depend on the applied magnetic field strength. The central magnetic field is preferably 30-100mT. The ratio of magnetic field strength to plasma discharge power is preferably 2-4mT / W.

[0037] The sliding resistance range is preferably 1-5Ω.

[0038] The gas collection and utilization device and the liquid collection and utilization device depend on the application site and can be a steel cylinder, a storage tank, or a fuel cell, etc.

[0039] The gas mixing tank is used for raw material supply. The raw materials can be one of CO2+H2, CO2+CH4, and CO2+H2O.

[0040] A mass flow meter is arranged on the gas inlet pipeline a to control the reaction flow rate. The flow rate range can be selected from 0-3L / min.

[0041] A method for processing CO2 to prepare liquid fuel, using the device described above, comprises the following steps:

[0042] In step (1), the power supply / gas unit preferably uses renewable energy. A solar panel is connected to an energy storage battery through a controller. The stored electrical energy is boosted to 220V by an inverter and then stably output. A gas mixing tank is connected to a ball valve, which is connected in series with an insulated pipeline a to make the gas enter the hollow metal electrode of the reactor.

[0043] Step (2), the magnetic hydrophobic catalyst is loaded at the bottom of the reactor cavity in the plasma fluidized bed unit, the hollow metal electrode is embedded in the insulation sleeve as a high-voltage electrode and a gas inlet, the tail is inserted into the coaxial buckle, and the tail blowing connector is used as a gas outlet to form a fluidized bed reactor with the reactor cavity, and preliminary fluidization is realized through flow rate control; the circulating water machine is connected with the water inlet and the water outlet through the circulating water pipeline, and the water inlet and the water outlet are grounded respectively, and the circulating water interlayer temperature is controlled by the circulating water machine; the plasma power supply is connected with the hollow metal electrode through a high-voltage input line to generate stable plasma discharge;

[0044] Step (3), in the magnetic control unit, the permanent magnet is embedded in the electromagnetic coil, and two groups of magnets are placed in parallel to form a stable magnetic field in the middle, the distance between the upper and lower magnets is adjusted by the movable support, the magnet and the sliding resistance are connected in series, the loop current and voltage are controlled by the direct current driving power supply, and the magnetic field strength is adjusted, so that the catalyst is stably fluidized.

[0045] Step (4), in the fuel collection unit, the gas-liquid separator is arranged in the condensation tank, and is further connected with the gas collection and utilization device and the liquid collection and utilization device to form a fuel collection system.

[0046] The technical advantages of the present application are that:

[0047] (1) The specific magnetic solid particles are stably suspended and fluidized by the double regulation of the reactor bottom flow field and the parallel Lorentz force of the electromagnetic field, without introducing the radial magnetic field, and the central parallel magnetic field and the two-end permanent magnet do not affect the plasma discharge;

[0048] (2) The reactor matches the special functional magnetic hydrophobic catalyst, which can produce stable fluidization effect under the condition of containing water, and fully improve the adhesion phenomenon between particles, effectively promote the conversion of CO2 and the separation of H2O;

[0049] (3) The circulating water medium is used for cooling the discharge conversion area, the reaction balance of CO2 conversion is moved to the direction of high-value liquid fuel, and the selectivity of by-products is reduced;

[0050] (4) The present application has the advantages of simple structure, low energy consumption, direct use of renewable energy, controllable discharge strength and reaction temperature, large processing flux and high selectivity of liquid fuel. BRIEF DESCRIPTION OF DRAWINGS

[0051] The drawings accompanying the specification of the present application are used to provide further understanding of the present application, the illustrative embodiments of the present application and the description thereof are used to explain the present application, and do not constitute limitation of the present application.

[0052] Figure 1 It is the front view of the overall device structure in the embodiment of the present application;

[0053] Figure 2 Figure 1 is a schematic diagram of a three-dimensional structure of a plasma fluidized bed reactor and a magnetic field regulation direction according to the present application.

[0054] Figure 3 Figure 2 is a comparison chart of CO2 conversion performance of the plasma fluidized bed reactor and the fixed bed reactor according to the present application.

[0055] The reference signs shown in the drawings are as follows:

[0056] 1 solar panel, 2 controller, 3 energy storage battery, 4 inverter, 5 plasma power supply, 6 high-voltage input line, 7 insulating pipeline a, 8 ball valve, 9 gas mixing tank, 10 hollow metal electrode, 11 insulating sleeve, 12 gas outlet, 13 reactor cavity, 14 permanent magnet, 15 direct current driving power supply, 16 movable support, 17 circulating water interlayer, 18 magnetic hydrophobic catalyst, 19 circulating water machine, 20 sliding resistor, 21 electromagnetic coil, 22 tail blowing joint, 23 coaxial buckle, 24 circulating water pipeline, 25 insulating pipeline b, 26 gas-liquid separator, 27 condensation tank, 28 gas collection and utilization device, 29 liquid collection and utilization device. DETAILED DESCRIPTION

[0057] All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs.

[0058] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit exemplary embodiments according to the present application. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, devices, components, and / or combinations thereof, but do not preclude the presence or addition of one or more other features, steps, operations, devices, components, and / or combinations thereof.

[0059] In one exemplary embodiment of the present application, as Figure 1 2 ​As shown, a circulating water type plasma magnetically stabilized fluidized bed conversion device mainly comprises a solar panel 1, a controller 2, an energy storage battery 3, an inverter 4, a plasma power supply 5, a high-voltage input line 6, an insulating pipeline a 7, a ball valve 8, a gas mixing tank 9, a hollow metal electrode 10, an insulating sleeve 11, a gas outlet 12, a reactor cavity 13, a permanent magnet 14, a direct current driving power supply 15, a movable support 16, a circulating water jacket 17, a magnetic hydrophobic catalyst 18, a circulating water machine 19, a sliding resistor 20, an electromagnetic coil 21, a tail blow joint 22, a coaxial buckle 23, a circulating water pipeline 24, an insulating pipeline b 25, a gas-liquid separator 26, a condensation tank 27, a gas collection and utilization device 28, and a liquid collection and utilization device 29. The solar panel 1 is sequentially connected with the controller 2, the energy storage battery 3, and the inverter 4. The first output end of the inverter 4 is sequentially connected with the plasma power supply 5, the high-voltage input line 6, and the hollow metal electrode 10. The second output end of the inverter 4 is sequentially connected with the direct current driving power supply 15, the sliding resistor 20, and the electromagnetic coil 21. The gas mixing tank 9 is sequentially connected with the ball valve 8, the insulating pipeline a 7, and the hollow metal electrode 10. The top of the reactor cavity 13 is covered with the insulating sleeve 11. The upper part of the reactor cavity 13 is provided with the gas outlet 12. The gas outlet 12 is sequentially connected with the insulating pipeline b 25 and the gas-liquid separator 26. The gas-liquid separator 26 is placed in the condensation tank 27. The top of the gas-liquid separator 26 is connected with the gas collection and utilization device 28. The lower part of the gas-liquid separator 26 is connected with the liquid collection and utilization device 29. The hollow metal electrode 10 extends into the reactor cavity 13 through the insulating sleeve 11. The outer periphery of the reactor cavity 13 is provided with the circulating water jacket 17. The top water outlet of the circulating water jacket 17 is connected with the upper water inlet of the circulating water machine 19. The lower water outlet of the circulating water machine 19 is sequentially connected with the circulating water pipeline 24 and the water inlet of the circulating water jacket 17. The lower part of the reactor cavity 13 is provided with the coaxial buckle 23, which fixes the tail part of the hollow metal electrode 10. The bottom of the hollow metal electrode 10 is provided with the tail blow joint 22.

[0060] The outer upper end of the reactor cavity 13 is sequentially sleeved with the permanent magnet 14 and the electromagnetic coil 21 from inside to outside. The permanent magnet 14 is embedded in the electromagnetic coil 21. The outer lower end of the insulating sleeve 11 is sequentially sleeved with the permanent magnet 14 and the electromagnetic coil 21 from inside to outside. The permanent magnet 14 at the outer upper end of the insulating sleeve 11 and the permanent magnet 14 at the outer lower end of the insulating sleeve 11 are fixedly connected through the movable support 16. The magnetic hydrophobic catalyst 18 is arranged in the middle part of the reactor cavity 13. The permanent magnet 14 is embedded in the electromagnetic coil 21, constituting a magnet.

[0061] A circulating water type plasma magnetically stabilized fluidized bed conversion device comprises four units, wherein,

[0062] The solar panel 1, the controller 2, the energy storage battery 3, the inverter 4, the gas mixing tank 9, the ball valve 8, and the insulating pipeline a 7 jointly constitute a power / gas supply unit;

[0063] Plasma power supply 5, high voltage input line 6, reactor cavity 13, insulating sleeve 11, magnetic hydrophobic catalyst 18, hollow metal electrode 10, coaxial buckle 23, tail blow joint 22, circulating water machine 19, circulating water pipeline 24, circulating water sandwich 17 constitute the plasma fluidized bed unit;

[0064] DC drive power supply 15, sliding resistance 20, permanent magnet 14, electromagnetic coil 21, movable support 16 together constitute the magnetic control unit;

[0065] Insulating pipeline b25, gas-liquid separator 26, condenser tank 27, gas collection and utilization device 28 and liquid collection and utilization device 29 constitute the fuel collection unit.

[0066] The solar panel 1 is used for converting solar energy into direct current, and the output voltage is 18V and the power is 1000W.

[0067] The controller 2 is adapted to the current of 60A.

[0068] The energy storage battery 3 is used for storing the electric energy converted by the solar panel 1, the input and output voltage of the battery is set to 12V, and the capacity is 400Ah.

[0069] The inverter 4 is used for inverting the direct current output by the energy storage battery 3 into 220V alternating current, and the power is 5500W.

[0070] The plasma power supply 5 is used for exciting discharge plasma, the power supply is selected as nanosecond pulse source, the output voltage is 15kV, the rising edge is 100ns, the falling edge is 200ns, the frequency is 7kHz, and the pulse width is 3000ns.

[0071] The high voltage input line 6 has a withstand voltage of 20kV.

[0072] The reactor cavity 13 is made of quartz, and the insulating sleeve 11 and the coaxial buckle 23 are made of polytetrafluoroethylene.

[0073] The hollow metal electrode 10 is used as a high voltage input end and an air inlet end, and is made of stainless steel.

[0074] The magnetic hydrophobic catalyst 18 is MgO-Al2O3 composite metal oxide carrier loaded with nano-Ni component, and the mass fraction of the nano-Ni component is 40% based on the total mass of the catalyst. The magnetic particle size in the magnetic hydrophobic catalyst is 10 nm. The magnetic hydrophobic catalyst is prepared by using a hydrotalcite precursor method (MMgAl-LDH, M=Ni) and a calcination reduction process to prepare a non-magnetic carrier loaded magnetic catalyst a, the magnetic component is Ni, and the non-magnetic carrier is a mixed oxide of MgO-Al2O3 (the molar ratio of MgO:Al2O3 is 1:1); the prepared magnetic catalyst a is mixed with polytetrafluoroethylene at a mass ratio of 1:1 to obtain the magnetic hydrophobic catalyst 18, and the particle size of the magnetic hydrophobic catalyst 18 is preferably 80-100 mesh.

[0075] The outlet aperture of the tail blow joint 22 is selected to be 1 mm, and the fluidization air speed is 1 L / min / g.

[0076] The circulating water pipeline 24 is made of polyurethane and is used for gas supply or liquid circulation;

[0077] The circulating water interlayer 17 is provided with a water inlet and a water outlet and forms a circulating water circuit with the circulating water machine 19, and the water enters from the bottom and exits from the top, and tap water is selected, and the temperature is set to 10°C.

[0078] The direct current driving power supply 15 has a voltage range of 0-60V, a current of 0-20A, and a power range that can be adjusted;

[0079] The permanent magnet 14 is made of ferrite material, and the central magnetic field strength is about 30 mT;

[0080] The electromagnetic coil 21 is a copper coil with 1000 turns and a diameter of 1 mm, and the magnetic field after energization is about 60 mT, and the ratio of magnetic field strength to plasma discharge power is 2.5 mT / W;

[0081] The sliding resistance 20 is 1Ω;

[0082] The gas collection and utilization device 28 and the liquid collection and utilization device 29 are storage tanks;

[0083] The gas mixing tank 9 is used for raw material supply, and the raw material is CO2+H2 with a ratio of 1:3;

[0084] The mass flow meter in the gas inlet path controls the reaction flow rate to be 500 mL / min.

[0085] A method for treating CO2 to prepare liquid fuel using a circulating water type plasma magnetically stabilized fluidized bed conversion device as described above, comprising the following steps:

[0086] In step (1), the power supply / gas unit connects the solar panel 1 and the energy storage battery 3 through the controller 2. The stored electrical energy is boosted to 220V by the inverter 4 and then output stably. The gas supply section depressurizes the gas (volume ratio CO2:H2=1:3) in the mixing tank 9 and outputs it through the insulated pipeline a7. The flow rate is controlled to be 500mL / min by the ball valve 8 and the flow meter.

[0087] In step (2), a magnetic hydrophobic Ni / MgO-Al2O3 catalyst is packed into the bottom of the reactor cavity 13 in the plasma fluidized bed unit. The hollow metal electrode 10 serves as the high-voltage electrode and the air inlet, and is embedded in the insulating sleeve 11. The tail end is inserted into the coaxial buckle 23. The tail blow connector 22 serves as the air outlet and forms a fluidized bed reactor with the reactor cavity 13. Initial fluidization is achieved by controlling the flow rate. The circulating water machine 19 is connected to the inlet and outlet of the circulating water jacket 17 through the circulating water pipeline 24, and the inlet and outlet are grounded respectively. The temperature is controlled by the circulating water machine 19 and set to 10℃. The plasma power supply 5 is connected to the hollow metal electrode through the high-voltage input line 6 to generate stable plasma discharge.

[0088] In step (3), permanent magnet 14 is embedded in electromagnetic coil 21 in the magnetic control unit, and two sets are placed in parallel to form a stable magnetic field in the middle. The distance between the upper and lower magnets is controlled by the movable bracket 16. Electromagnetic coil 21 is connected in series with sliding resistor 20. The current and voltage of the control circuit are controlled by DC drive power supply to regulate the magnetic field strength and finally generate stable fluidization.

[0089] In step (4), the gas-liquid separator 26 is placed in the condensation tank 27 in the fuel collection unit, and the generated products are further connected to the gas collection and utilization device 28 and the liquid collection and utilization device 29 to form a fuel collection system to realize product collection.

[0090] like Figure 3 As shown, the CO2 conversion efficiency of the circulating water-type magnetically stabilized plasma fluidized bed converter of this invention is significantly higher than that of the fixed-bed reactor (comparative example). In conversion experiments using current parameters, the CO2 conversion rate exceeds 11% at high space velocities, while the fixed bed only achieves 4.4%. Specifically, chromatographic analysis revealed that the main component of the liquid fuel is methanol, with a methanol yield as high as 4.5%, compared to only 1.78% in the fixed bed. This demonstrates that this invention can significantly improve the yield of a single liquid fuel. Through magnetically stabilized fluidization technology combined with a dedicated catalyst, the synergy between plasma and catalyst can be effectively enhanced, and reaction energy consumption can be reduced, demonstrating significant technical advantages. The only difference between the CO2 conversion reaction conditions of the fixed-bed reactor and the CO2 conversion of the circulating water-type magnetically stabilized plasma fluidized bed converter of this invention is that the comparative example uses a fixed-bed reactor; all other reaction conditions are the same.

[0091] The application realizes stable suspension and fluidization of specific magnetic solid particles through double regulation of fluidized bed reactor bottom flow field and parallel Lorentz force of electromagnetic field, without introducing radial magnetic field, the temperature of fluidized bed reactor, plasma discharge and magnetic field intensity can be independently adjusted, effectively avoiding the interference of magnetic field on plasma, and circulating water cooling is introduced to reduce the reaction temperature and improve the fuel selectivity; the magnetic hydrophobic catalyst is a high hydrophobic supported magnetic catalyst.

[0092] The part of the application which is not described in detail belongs to the known technology of the person skilled in the art. The above-described embodiments only describe the preferred embodiments of the application, and the preferred embodiments do not describe all the details and limit the application to the specific embodiments. Without departing from the design spirit of the application, various modifications and improvements of the technical solutions of the application made by the person skilled in the art shall fall within the protection scope determined by the claims of the application.

Claims

1. A circulating water plasma magnetically stabilized fluidized bed conversion apparatus characterized by: The stable suspension and fluidization of magnetic solid particles are realized by the double regulation of the reactor bottom flow field and the parallel Lorentz force of the electromagnetic field, without introducing a radial magnetic field, the reactor temperature, plasma discharge and magnetic field strength can be independently adjusted, avoiding the interference of the magnetic field on the plasma, while the circulating water cooling is introduced to reduce the reaction temperature and improve the fuel selectivity; The magnetic solid particles are high-hydrophobic supported magnetic catalysts; The device comprises a solar cell panel (1), a controller (2), an energy storage battery (3), an inverter (4), a plasma power supply (5), a ball valve (8), a gas mixing tank (9), a hollow metal electrode (10), an insulating sleeve (11), an air outlet (12), a reactor cavity (13), a permanent magnet (14), a direct current driving power supply (15), a movable support (16), a circulating water jacket (17), a magnetic hydrophobic catalyst (18), a circulating water machine (19), a sliding resistance (20), an electromagnetic coil (21), a tail blow connector (22), a coaxial buckle (23), a gas-liquid separator (26), a condensation tank (27), a gas collection and utilization device (28) and a liquid collection and utilization device (29); The solar cell panel (1) is sequentially connected with the controller (2), the energy storage battery (3) and the inverter (4); the first output end of the inverter (4) is sequentially connected with the plasma power supply (5) and the hollow metal electrode (10); The second output end of the inverter (4) is sequentially connected with the direct current driving power supply (15), the sliding resistance (20) and the electromagnetic coil (21); the gas mixing tank (9) is sequentially connected with the ball valve (8) and the hollow metal electrode (10); The top of the reactor cavity (13) is covered with the insulating sleeve (11); the upper part of the reactor cavity (13) is provided with the air outlet (12); the air outlet (12) is connected with the gas-liquid separator (26); the gas-liquid separator (26) is placed in the condensation tank (27); the top of the gas-liquid separator (26) is connected with the gas collection and utilization device (28); the lower part of the gas-liquid separator (26) is connected with the liquid collection and utilization device (29); The hollow metal electrode (10) penetrates through the insulating sleeve (11) and extends into the reactor cavity (13); the outer periphery of the reactor cavity (13) is provided with the circulating water jacket (17); the top water outlet of the circulating water jacket (17) is connected with the upper water inlet of the circulating water machine (19); the lower water outlet of the circulating water machine (19) is connected with the water inlet of the circulating water jacket (17); the lower part of the reactor cavity (13) is provided with the coaxial buckle (23), which fixes the tail part of the hollow metal electrode (10); the bottom of the hollow metal electrode (10) is provided with the tail blow connector (22); The outer upper end of the reactor cavity (13) is sequentially sleeved with a permanent magnet (14) and an electromagnetic coil (21) from inside to outside; the outer lower end of the insulating sleeve (11) is sequentially sleeved with a permanent magnet (14) and an electromagnetic coil (21) from inside to outside; the permanent magnet (14) at the outer upper end of the insulating sleeve (11) and the permanent magnet (14) at the outer lower end of the insulating sleeve (11) are fixedly connected through a movable support (16); a magnetic hydrophobic catalyst (18) is arranged in the middle of the reactor cavity (13).

2. The apparatus of claim 1, wherein, The plasma power supply (5) and the hollow metal electrode (10) are connected through a high-voltage input line (6); the ball valve (8) and the hollow metal electrode (10) are connected through an insulating pipeline a (7); the gas outlet (12) is connected with the gas-liquid separator (26) through an insulating pipeline b (25); the lower water outlet of the circulating water machine (19) is connected with the water inlet of the circulating water interlayer (17) through a circulating water pipeline (24).

3. The apparatus of claim 1, wherein, The permanent magnet (14) at the outer upper end of the insulating sleeve (11) and the permanent magnet (14) at the outer lower end of the insulating sleeve (11) are placed in parallel.

4. The apparatus of claim 1, wherein, The permanent magnet (14) is embedded in the electromagnetic coil (21).

5. The apparatus of claim 2, wherein, The device comprises a power / gas supply unit, a plasma fluidized bed unit, a magnetic control unit and a fuel collection unit; the power supply part of the power / gas supply unit comprises a solar cell panel (1), a controller (2), an energy storage battery (3) and an inverter (4); the gas supply part comprises a gas mixing tank (9), a ball valve (8) and an insulating pipeline a (7); The plasma fluidized bed unit comprises a plasma power supply (5), a high-voltage input line (6), a reactor cavity (13), an insulating sleeve (11), a magnetic hydrophobic catalyst (18), a hollow metal electrode (10), a coaxial buckle (23), a tail blowing joint (22), a circulating water machine (19), a circulating water pipeline (24) and a circulating water interlayer (17); The magnetic control unit comprises a direct current driving power supply (15), a sliding resistor (20), a permanent magnet (14), an electromagnetic coil (21) and a movable support (16); The fuel collection unit comprises an insulating pipeline b (25), a gas-liquid separator (26), a condensation tank (27), a gas collection and utilization device (28) and a liquid collection and utilization device (29).

6. A method for processing CO2 to produce liquid fuel, characterized in that, The method comprises the following operation steps using the device of claim 5: Step (1), in the power / gas supply unit, the solar cell panel (1) is connected with the energy storage battery (3) through the controller; the stored electric energy is boosted to 220V through the inverter (4) and then stably output; the gas mixing tank (9) is connected with the ball valve (8), and then connected with the insulating pipeline a in series to make the gas enter the hollow metal electrode (10) of the reactor; Step (2), the magnetic hydrophobic catalyst (18) is filled in the bottom of the reactor cavity (13) in the plasma fluidized bed unit, the hollow metal electrode (10) is used as a high-voltage electrode and an air inlet path, is embedded in the insulating sleeve (11), and the tail is inserted into the coaxial buckle (23); the tail blowing connector (22) is used as an air outlet and is connected with the reactor cavity (13) to form a fluidized bed reactor, and preliminary fluidization is realized by controlling the flow rate; the circulating water machine (19) is connected with the water inlet and the water outlet of the circulating water sandwich (17) through the circulating water pipeline (24), and the water inlets and outlets are grounded respectively; the circulating water sandwich (17) temperature is controlled by the circulating water machine (19); the plasma power supply (5) is connected with the hollow metal electrode through the high-voltage input line (6) to generate stable plasma discharge; Step (3), the permanent magnet (14) is embedded in the electromagnetic coil (21) in the magnetic control unit, and two groups of the permanent magnets are placed in parallel to form a stable and constant magnetic field in the middle; the electromagnetic coil (21) and the sliding resistance (20) are connected in series, the loop current and voltage are controlled through the direct current driving power supply (15), the magnetic field strength is adjusted, and finally the catalyst is stably fluidized; Step (4), the gas-liquid separator (26) is placed in the condensation tank (27) in the fuel collection unit, and is further connected with the gas collection and utilization device (28) and the liquid collection and utilization device (29) to form a fuel collection system.

7. The method of claim 6, wherein, The hollow metal electrode (10) is used as a high-voltage input end and an air inlet end, the material of the hollow metal electrode (10) is aluminum, iron, copper or stainless steel, the outlet aperture of the tail blowing connector (22) is 1-2 mm, the air inlet flow rate is 0-5 L / min, and the fluidized air speed is 1 L / min / g-3 L / min / g.

8. The method of claim 6, wherein, The magnetic hydrophobic catalyst is prepared by using a hydrotalcite precursor method, supplemented by a calcination reduction process, and is a magnetic catalyst loaded on a non-magnetic carrier; the magnetic component is Fe, Co or Ni single component or several combinations; the non-magnetic carrier is a mixed oxide of MgO-Al2O3; the mass ratio of the prepared magnetic catalyst loaded on the non-magnetic carrier and the hydrophobic agent is 0.5-2.

9. The method of claim 8, wherein, The hydrophobic agent is polytetrafluoroethylene; the permanent magnet is made of rubidium iron boron, samarium cobalt or ferrite material; the sliding resistance is 1-5 Ω; the electromagnetic coil is a copper coil, the central magnetic field is 30-100 mT, and the ratio of the magnetic field strength to the plasma discharge power is 2-4 mT / W.

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