Cascading carbon sequestration device for multiple high-voltage electrode reaction kettles and control method of cascading carbon sequestration device

Abstract

The invention discloses a multi-high-voltage electrode reaction kettle cascade carbon sequestration device and a control method thereof. The multi-high-voltage electrode reaction kettle cascade carbon sequestration device comprises a high-voltage main reaction electrode kettle device, a gas supply electrode kettle device, a solvent supply electrode kettle device, a solid organic matter supply electrode kettle device and a product receiving electrode kettle device. Each supply electrode kettle device is respectively connected with the high-voltage main reaction electrode kettle device, and a supply material is conveyed to the high-voltage main reaction electrode kettle device through each supply electrode kettle device; the high-voltage main reaction electrode kettle device, the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device are respectively connected with the product receiving electrode kettle device, and products and supply materials after the reaction of the high-voltage main reaction electrode kettle device are conveyed to the product receiving electrode kettle device. The device not only can improve the reaction efficiency among molecules in the hydrothermal reaction process, but also does not involve the use of a catalyst, can efficiently convert gases such as carbon dioxide, ammonia gas and the like at low energy, and is simple in operation process and suitable for industrial production.

Description

Technical Field

[0001] The present application relates to the technical field of hydrothermal liquefaction, and mainly to a device for cascading carbon fixation of multiple high-voltage electrode reactors and a control method thereof. Background Art

[0002] With the continuous development of technology, many methods of carbon and nitrogen fixation have emerged, such as biological carbon fixation, soil carbon fixation and biological nitrogen fixation. Among them, hydrothermal carbon fixation / nitrogen fixation is a process that uses a high temperature and high pressure hydrothermal environment to heat water and carbon dioxide and nitrogen to convert them into compounds such as formic acid, methanol, nitrite and nitrate.

[0003] The critical point of water molecules under supercritical conditions is 374.3℃ / 22.1MPa. The angle between the 2H atom and the oxygen atom in the water molecule under high temperature and high pressure increases from 104.5° to 180°. The change in its structure causes a change in its chemical properties. With the disappearance of polarity, it can dissolve most organic matter. The supercritical conditions of carbon dioxide and nitrogen are 32℃ / 7.4MPa and -147℃ / 3.4MPa, respectively, which means that when water molecules enter the supercritical state, carbon dioxide and nitrogen also enter the supercritical state. On the other hand, larger clusters will form between molecules in the supercritical state. The higher the temperature and pressure, the larger the clusters. For example, the formation of water clusters will hinder the collision between water molecules and carbon dioxide and nitrogen. Increasing intermolecular collisions and reducing the size of clusters have become urgent problems to be solved in the hydrothermal method. In addition, the high energy consumption and low conversion efficiency of the traditional hydrothermal method have greatly limited its application.

[0004] In summary, it is of great significance to develop a high-pressure electrode reactor cascade carbon and nitrogen fixation device with low energy consumption and high heating efficiency. Summary of the invention

[0005] In response to the problems of high energy consumption, low conversion efficiency and molecular clustering in the hydrothermal technology in the prior art, the present application proposes a device for cascading carbon fixation with multiple high-voltage electrode reactors and a control method thereof, which can continuously produce products such as small molecule acids, alcohols and aldehydes.

[0006] According to one aspect of the present invention, a device for cascading carbon fixation of multiple high-voltage electrode reactors is proposed, comprising: a high-voltage main reaction electrode reactor device, a gas supply electrode reactor device, a solvent supply electrode reactor device, a solid organic matter supply electrode reactor device and a product receiving electrode reactor device. The gas supply electrode reactor device, the solvent supply electrode reactor device and the solid organic matter supply electrode reactor device are respectively connected to the high-voltage main reaction electrode reactor device, and the supply material is transported to the high-voltage main reaction electrode reactor device through each of the supply electrode reactor devices, wherein the gas supply electrode reactor device provides supercritical gas (such as carbon dioxide and nitrogen, etc.) and super / subcritical water; the solvent supply electrode reactor device provides supercritical gas and super / subcritical high-pressure solvent; the solid organic matter supply electrode reactor device liquefies solid organic matter (such as biomass and plastics) and then provides supercritical gas and super / subcritical high-pressure solvent. The high-pressure main reaction electrode kettle device, the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device are respectively connected to the product receiving electrode kettle device, and the product and supply material after the reaction of the high-pressure main reaction electrode kettle device are transported to the product receiving electrode kettle device.

[0007] In a specific embodiment, the device can obtain different main products, such as acid, alcohol or aldehyde, or multiple products coexisting, such as aldehyde / alcohol, acid / aldehyde, and alcohol, aldehyde and acid coexisting in a certain proportion, by changing the gas, solvent and solid organic composition in the reactor in the experiment, as well as the reaction parameters such as temperature and pressure in the reactor. When the main product is determined, or multiple products coexist, the composition and proportion of the gas and solvent in the main reactor can be determined by the proportion of C, H, O, and N in the product, and then the composition and proportion of the gas, solvent and solid organic matter in the gas supply electrode reactor device, the solvent supply electrode reactor device and the solid organic matter supply electrode reactor device can be determined.

[0008] In a specific embodiment, each supply electrode auxiliary device provides the following reaction raw materials to the high-voltage main reaction electrode kettle device: the gas supply electrode kettle device provides C, N, O and H sources, wherein the proportion of C is about 10-30%, and the proportion of N is about 1-20%; the solvent supply electrode kettle device provides C and H sources, and in order to prevent violent reactions, appropriate water and carbon dioxide are added; the solid organic matter supply electrode kettle device provides C and H sources.

[0009] In a specific embodiment, although the ratio of C, H, O, and N products in the main reactor is the same as the ratio of the target product, the reaction rate between C and H and O is much lower than that between O and H and OH, so the main product is mainly H2O. In order to increase the content of the target product, it is necessary to increase the content of C or N appropriately, thereby increasing the collision frequency between C and H, C and N, and N and O. However, too high a C content is likely to cause carbon deposition to block the channel. Therefore, setting the ratio of C, H, O, and N products in the high-voltage main reaction electrode reactor device to be the same as the ratio of the target product, and then increasing the C content appropriately through the solvent and solid organic matter supply electrode reactor device can ensure that there is sufficient C source in the main reactor without excessive C, thereby avoiding carbon deposition, and the influence range of the C percentage content of the final product is 0.0001-0.1% (mol%).

[0010] Preferably, the electrode kettle device includes an external insulation layer and a reactor cavity; the reactor cavity includes a reactor liner, an electrode assembly, an air inlet, an exhaust port, a liquid inlet, a liquid outlet, a safety valve, a pressure sensor and a temperature sensor.

[0011] In a specific embodiment, the air inlet, the air outlet, the liquid inlet and the liquid outlet are all connected to the needle valve by a metal tube, and the liquid outlet is provided with a filter screen.

[0012] In a specific embodiment, the autoclave reaction chamber is cylindrical, with a diameter of 10-50 cm and a thickness of more than 5 mm, and is made of one of stainless steel, tungsten and tungsten-molybdenum alloy.

[0013] In a specific embodiment, the electrode assembly includes an insulating ceramic plate and an electrode, wherein the electrode material includes one or more of graphene, carbon, iridium-rhenium, and tungsten-rhenium-iridium-potassium alloy.

[0014] In a specific embodiment, the inner container of the reaction kettle is made of insulating inert inorganic materials such as ceramics and corundum.

[0015] Preferably, the gas supply electrode kettle device comprises a gas chamber 1 and a gas chamber 2, and the gas chamber 1 and the gas chamber 2 are independent electrode kettle devices; the gas chamber 1 and the gas chamber 2 are connected through an inter-chamber transfer channel I.

[0016] In a specific embodiment, the ratio and content of gas and water in the gas supply electrode kettle device are determined by the percentage content of O in the product. In the ratio of the target products O, C, H, and N, O mainly comes from gas and water. The molar ratio of gas and water can be calculated from the percentage content of the target products O, C or O, N, that is, the amount of input gas can be calculated when the water content is constant. Therefore, when the volume of the reactor is fixed and the water content is 1 / 10-1 / 2 of the volume of the reactor, the input gas content is fixed and the initial pressure is also fixed. C is mainly provided by carbon dioxide, N is provided by N2, or NH3, NOx combined with each other, or H is provided by water. After the ratio and content of CO2, N2 and H2O are determined, in order to avoid carbon deposition, a chamber treatment is usually adopted. After the water and gas are injected into the gas chamber 1 and heated to a certain temperature, they are injected into the gas chamber 2 through the pipetting channel I. After the secondary discharge treatment, after adjusting the pressure in the chamber, they are injected into the high-pressure main reaction electrode kettle device, thereby avoiding the temperature and pressure instability (too low or too high) caused by carbon deposition affecting the product composition. In addition, the two air chambers can provide sufficient volume for outputting stable temperature and pressure.

[0017] Preferably, the solid organic matter replenishing electrode kettle device comprises a solid organic matter chamber 1 and a solid organic matter chamber 2, and the solid organic matter chamber 1 and the solid organic matter chamber 2 are independent electrode kettle devices; the solid organic matter chamber 1 and the solid organic matter chamber 2 are connected via an inter-chamber transfer channel II; the solid organic matter chamber 1 is also provided with a feed assembly, and a ventilation port, a sealing cover, a feed bin and a one-way ball valve are sequentially arranged in the feed assembly from top to bottom.

[0018] In a specific embodiment, the ratio and content of gas, solid organic powder, water and solvent in the solid organic matter supply electrode kettle device refer to the calculation method of the gas supply electrode kettle device. It should be noted that C mainly comes from solid organic matter, the solvent is used to adjust the ratio of C, H and O, CO2 mainly plays the role of adjusting the pressure in the reactor, and O and H mainly come from water and solid organic matter. In order to avoid carbon deposits caused by the injected organic solid powder blocking the output end, chamber processing is usually adopted. After the solid organic powder, solvent and gas are injected into the solid chamber 1 and heated to a certain temperature, they are injected into the solid chamber 2 through the pipetting channel II. After secondary heating and adjusting the pressure in the chamber, they are injected into the high-pressure main reaction electrode kettle device, thereby avoiding carbon deposition, temperature and pressure instability (too low or too high) affecting the product composition.

[0019] In a specific embodiment, the ratio of gas, water and solvent in the solvent supply electrode kettle device is determined by the difference in the ratio of C, H, O and N between the reaction product of the high-pressure main reaction electrode kettle device and the target product after the gas and solid organic matter supply electrode kettle device are simultaneously output to the high-pressure main reaction electrode kettle device. The required content of C, H, O and N can be known, and then the corresponding ratio and content of gas, water and solvent can be given.

[0020] In a specific embodiment, the product receiving electrode kettle device mainly receives the product after the reaction of the high-pressure main reaction electrode kettle device is completed, and then refers to the ratio of the target product C, H, O, and N, and injects the output products of the solid organic matter replenishment electrode kettle device and the solvent replenishment electrode kettle device to fine-tune the element ratio and obtain the optimal parameters.

[0021] According to a second aspect of the present invention, a control method for a device for cascading carbon fixation of multiple high-voltage electrode reactors is provided, comprising the following steps:

[0022] S1. Determine the target product, prepare a solution and load it into each of the reaction kettle cavities, and apply voltage to each of the electrode assemblies through a plasma power supply;

[0023] S2, start the reaction, the high-pressure main reaction electrode kettle device delivers the reaction product to the product receiving electrode kettle device, and at the same time the gas supply electrode kettle device supplies most of the gas and part of the water to the high-pressure main reaction electrode kettle device, and the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device jointly supply the solvent and a small part of the gas to the high-pressure main reaction electrode kettle device;

[0024] S3. After a period of reaction, the product in each of the electrode kettle devices is taken for component and content analysis, and compared with the target product, the ratio and composition of the gas and solvent in each of the electrode kettle devices are adjusted by a single factor method, and then the temperature and pressure are adjusted, and finally the power supply parameters are changed to obtain the optimal parameters;

[0025] S4. Obtain the target product and complete the reaction.

[0026] Preferably, in S1, the voltage applied by the plasma power supply is 200-5000V, the frequency is 5Hz-1kHz, the output waveform includes one of a sine wave, a square wave and a pulse wave, and the output power is 100-20000W.

[0027] In a specific embodiment, after the current is stabilized to 0.05-1A, a stable discharge plasma is generated, and the gas and solvent react for a period of time (different solvents and different reactors have different reaction times) and then enter a subcritical or supercritical state.

[0028] Preferably, in S2, the replenishment principle of each replenishment electrode kettle device is: without affecting the main components of the product, the solid organic matter replenishment electrode kettle device is mainly used, followed by the gas replenishment electrode kettle device, and finally the solvent replenishment electrode kettle device. This replenishment principle can effectively control the cost of the reaction.

[0029] Preferably, in S2, when the electrode kettle devices exchange solutions with each other, the output amount is equal to the input amount. This principle can ensure that the pressure in the reactor remains unchanged when the electrode kettle devices exchange solutions, and will not cause the reactor to become unbalanced.

[0030] Further preferably, the rate of solution delivery satisfies the Navier-Stokes equations: ρ is density, u is flow velocity, t is time, ▽ is the Laplace operator, p is pressure, μ is viscosity coefficient, and g is gravitational acceleration.

[0031] In a specific embodiment, the solution transport between each electrode kettle device is determined by the rate at which the high-pressure main reaction electrode kettle device outputs the product, and the amount of the output product is less than 1 / 50 of the total solution amount. The flow rate can be known from the output pipe diameter and the pressure in the kettle. As long as the pressure, temperature, viscosity coefficient, output pipe diameter and output product flow rate in the high-pressure main reaction electrode kettle device are fixed, the output product flow rate can be obtained. If the pressure, temperature, density, viscosity coefficient and output pipe diameter in each supply electrode kettle device are known, the flow rate of each supply electrode kettle device injected into the high-pressure main reaction electrode kettle device can be calculated, and then the flow rate entering the high-pressure main reaction electrode kettle device can be obtained. In addition, the flow rate of each supply electrode kettle device must also meet the principle that C is mainly provided by carbon dioxide, biomass and plastics, N is mainly provided by nitrogen-containing gases (N2, NOx, etc.), H is mainly provided by water, and the supply of solvents is minimized.

[0032] Preferably, in S3, each time the parameters are adjusted, the product needs to be analyzed and tested, and compared with the target product to obtain the optimal reaction parameters.

[0033] In a specific embodiment, the adjustment parameters and adjustment methods are as follows: first, the ratio and content of carbon dioxide, water, nitrogen and organic matter are changed one by one at a certain temperature and pressure, wherein the gas content is adjusted by 0.1 MPa each time, and the content of water and solvent is adjusted by 0.01% (mol%) each time, and then the product composition and content are measured and analyzed to find the optimal ratio and content of carbon dioxide, water, nitrogen and organic matter; secondly, the temperature and pressure are adjusted, the temperature is adjusted by 5°C, or the pressure is adjusted by 0.1 MPa, and it is necessary to analyze the product composition and content to find the optimal temperature and pressure; finally, on the basis of the above, only the power supply parameters (duty cycle, frequency, rising edge, voltage and discharge current, etc.) are adjusted to finally obtain the optimal parameters.

[0034] The operating principle of the device of the present invention is as follows: when the electrode kettle device is working, the strong electric field generated by the potential difference between the two electrodes is used to drive the polar molecules near the electrode to move and heat the solution. As the solution temperature rises and gasifies, the pressure in the kettle increases, and the pressure increase causes the boiling point of the solution to increase. This cycle repeats itself, and the solution enters a subcritical / supercritical state. The polarity of polar molecules begins to weaken in the subcritical state, and the molecular polarity disappears in the supercritical state. At this time, 2-3 water molecule aggregates are the main form. When water molecules enter the supercritical state, CO2, N2, NH3 and NOx are already supercritical. Supercritical discharge easily obtains free radicals such as H, O, OH, C, CH, CH2, CH3, CO, NH and NH2. These free radicals, electrons, ions, water molecules, gas molecules and biomass / plastics frequently collide with each other, and many reactions that are difficult to achieve at normal temperature and pressure will occur. For example, carbon dioxide and water react to generate products such as formic acid, methanol, formaldehyde and acetic acid, and carbon dioxide, nitrogen and water react to generate products such as methylamine, urea, ammonia, nitrous acid and nitric acid. As the reaction products are input from the high-pressure main reaction electrode kettle device to the product receiving electrode kettle device, each supply electrode kettle device replenishes gas and solvent in time according to actual needs for continued reaction.

[0035] Compared with the prior art, the beneficial effects of this application are:

[0036] (1) The device of the present application can increase the kinetic energy of molecules during the hydrothermal reaction, causing frequent collisions between molecules and significantly reducing the size of clusters, thereby improving the reaction efficiency between molecules;

[0037] (2) The device of the present application can continuously generate reaction products by replenishing each supply electrode kettle device in real time;

[0038] (3) The device of the present application does not involve the use of catalysts in the reaction process and can efficiently and low-energy convert gases such as carbon dioxide and ammonia. The operation process is simple and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated into and constitute a part of this specification. The accompanying drawings illustrate the embodiments and are used together with the description to explain the principles of the present invention. It will be easy to recognize other embodiments and many expected advantages of the embodiments because they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale with each other. The same reference numerals refer to corresponding similar parts.

[0040] Figure 1 The overall structural schematic diagram of the cascade carbon fixation device with multiple high-voltage electrode reactors of the present invention is shown;

[0041] Figure 2 The schematic diagram of the structure of the high-voltage main reaction electrode kettle device of the present invention is shown;

[0042] Figure 3 The schematic diagram of the structure of the gas supply electrode kettle device of the present invention is shown;

[0043] Figure 4 The schematic diagram of the structure of the solvent supply electrode kettle device of the present invention is shown;

[0044] Figure 5 The schematic diagram of the structure of the solid organic matter supply electrode kettle device of the present invention is shown;

[0045] Figure 6 A schematic structural diagram of a solid feed assembly of the present invention is shown;

[0046] Figure 7 The structural schematic diagram of the feed bin of the present invention is shown;

[0047] Figure 8 The schematic diagram of the structure of the product receiving electrode kettle device of the present invention is shown;

[0048] Fig. 9 A flow chart of a control method for a cascaded carbon fixation device of multiple high-voltage electrode reactors according to the present invention is shown.

[0049] In the figure, 1-high-pressure main reaction electrode kettle device, 2-gas supply electrode kettle device, 3-solvent supply electrode kettle device, 4-solid organic matter supply electrode kettle device, 5-product receiving electrode kettle device, 6-insulation layer, 7-reactor cavity, 8-reactor liner, 9-electrode assembly, 10-safety valve, 11-temperature sensor, 12-pressure sensor, 13-filter, 101-liquid inlet 1 (main), 102-air inlet (main), 103-exhaust port (main), 104-liquid inlet 2 (main), 105-liquid outlet (main), 201-gas chamber 1, 202-gas chamber 2, 203-liquid inlet (gas 1), 204-exhaust port (gas 1), 205-air inlet (gas 1), 206-liquid transfer channel I, 207-exhaust port (gas 2), 208-air inlet (Gas 2), 209-Liquid outlet (Gas 2), 301-Liquid inlet (Liquid) 302-Exhaust port (Liquid), 303-Gas inlet (Liquid), 304-Liquid outlet (Liquid), 401-Solid chamber 1, 402-Solid chamber 2, 403-Feeding assembly, 403-1-Ventilation port, 403-2-Sealing cover, 403-3-Feeding bin, 403-4-One-way ball valve, 404-Inlet Liquid port (solid one), 405-exhaust port (solid one), 406-air inlet (solid one), 407-pipetting channel II, 408-exhaust port (solid two), 409 air inlet (solid two), 410-liquid outlet (solid two), 501-liquid inlet one (production), 502-exhaust port (production), 503-liquid inlet two (production), 504-liquid inlet three (production), 505-liquid outlet (production). DETAILED DESCRIPTION

[0050] The present application will be further described in detail below in conjunction with the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are only used to explain the relevant invention, rather than to limit the invention. It should also be noted that, for ease of description, only the parts related to the relevant invention are shown in the accompanying drawings.

[0051] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0052] Figure 1 The overall structural schematic diagram of the multiple high-voltage electrode reactor cascade carbon fixation device of the present invention is shown as follows: Figure 1 As shown, a device for cascading carbon fixation of multiple high-voltage electrode reactors includes: a high-voltage main reaction electrode reactor device 1, a gas supply electrode reactor device 2, a solvent supply electrode reactor device 3, a solid organic matter supply electrode reactor device 4 and a product receiving electrode reactor device 5. The gas supply electrode reactor device 2 provides supercritical gas (such as carbon dioxide and nitrogen, etc.) and super / subcritical water; the solvent supply electrode reactor device 3 provides supercritical gas and super / subcritical high-pressure solvent; the solid organic matter supply electrode reactor device 4 liquefies solid organic matter (such as biomass and plastic) and then provides supercritical gas and super / subcritical high-pressure solvent. The gas supply electrode reactor device 2, the solvent supply electrode reactor device 3 and the solid organic matter supply electrode reactor device 4 are respectively connected to the high-voltage main reaction electrode reactor device 1, and the supply material is transported to the high-voltage main reaction electrode reactor device 1 through each supply electrode reactor device. The high-pressure main reaction electrode kettle device 1, the solvent supply electrode kettle device 3 and the solid organic matter supply electrode kettle device 4 are respectively connected to the product receiving electrode kettle device 5, and the product and the supply material after the reaction of the high-pressure main reaction electrode kettle device 1 are transported to the product receiving electrode kettle device 5.

[0053] Figure 2 is a structural schematic diagram of the high-voltage main reaction electrode kettle device 1, such as Figure 2 As shown, the high-pressure main reaction electrode kettle device 1 includes: an insulation layer 6 and a reactor cavity 7; the reactor cavity 7 includes a reactor liner 8, an electrode assembly 9, a safety valve 10, a temperature sensor 11, a pressure sensor 12, a liquid inlet 1 (main) 101, an air inlet (main) 102, an exhaust port (main) 103, a liquid inlet 2 (main) 104 and a liquid outlet (main) 105, and a filter 13 is arranged in the liquid outlet (main) 105.

[0054] Figure 3 is a schematic diagram of the structure of the gas supply electrode kettle device 2, as shown in Figure 3As shown, the gas supply electrode kettle device 2 is divided into a gas chamber 1 201 and a gas chamber 202, both of which are provided with a thermal insulation layer 6 and a reactor cavity 7, and the reactor cavity 7 is provided with a reactor liner 8, an electrode assembly 9, a safety valve 10, a temperature sensor 11 and a pressure sensor 12; wherein, the gas chamber 1 201 is also provided with a liquid inlet (gas 1) 203, an exhaust port (gas 1) 204 and an air inlet (gas 1) 205, and the gas chamber 2 is also provided with an exhaust port (gas 2) 207, an air inlet (gas 2) 208 and a liquid outlet (gas 2) 209, the gas chamber 1 201 and the gas chamber 2 202 are connected by a pipetting channel I 206, and a filter 13 is provided in the liquid outlet (gas 2) 209.

[0055] Figure 4 is a schematic diagram of the structure of the solvent supply electrode kettle device 3, as shown in Figure 4 As shown, the solvent supply electrode kettle device 3 includes: an insulation layer 6 and a reactor cavity 7; the reactor cavity 7 includes a reactor liner 8, an electrode assembly 9, a safety valve 10, a temperature sensor 11, a pressure sensor 12, a liquid inlet (liquid) 301, an exhaust port (liquid) 302, an air inlet (liquid) 303 and a liquid outlet (liquid) 304, and a filter 13 is arranged in the liquid outlet (liquid) 304.

[0056] Figure 5 It is a structural schematic diagram of the solid organic matter supply electrode kettle device 4, as shown in Figure 5 As shown, the solid organic matter replenishing electrode kettle device 4 is divided into a solid chamber 1 401 and a solid chamber 2 402, both of which are provided with a heat preservation layer 6 and a reactor cavity 7, and the reactor cavity 7 is provided with a reactor liner 8, an electrode assembly 9, a safety valve 10, a temperature sensor 11 and a pressure sensor 12; wherein, the solid chamber 1 401 is also provided with a feed assembly 403, a liquid inlet (solid 1) 404, an exhaust port (solid 1) 405 and an air inlet (solid 1) 406, and the solid chamber 2 is also provided with an exhaust port (solid 2) 408, an air inlet (solid 2) 409 and a liquid outlet (solid 2) 410, and the solid chamber 1 401 and the solid chamber 2 402 are connected by a pipetting channel II 407, and a filter screen 13 is provided in the pipetting channel II 407 and the liquid outlet (solid 2) 410.

[0057] Figure 6 is a schematic structural diagram of the feed assembly 403, Figure 7 It is a schematic diagram of the structure of the feed bin 403-3. Figure 6 As shown, the feed assembly 403 includes a ventilation port 403-1, a sealing cover 403-2, a feed bin 403-3 and a one-way ball valve 403-4.

[0058] Figure 8 is a schematic diagram of the structure of the product receiving electrode kettle device 5, as shown in Figure 8As shown, the product receiving electrode kettle device 5 includes: an insulation layer 6 and a reactor cavity 7; the reactor cavity 7 includes a reactor liner 8, an electrode assembly 9, a safety valve 10, a temperature sensor 11, a pressure sensor 12, a liquid inlet 1 (production) 501, an exhaust port (production) 502, a liquid inlet 2 (production) 503, a liquid inlet 3 (production) 504 and a liquid outlet (production) 505, and a filter 13 is arranged in the liquid outlet (production) 505.

[0059] Among them, the liquid inlet 1 (main) 101 and the liquid inlet 1 (production) 501 are respectively connected to the liquid outlet (liquid) 304 to receive the material supply of the solvent supply electrode kettle device 3; the gas inlet (main) 102 is connected to the liquid outlet (gas 2) 209 to receive the material supply of the gas supply electrode kettle device 2; the liquid inlet 2 (main) 104 and the liquid inlet 3 (production) 504 are respectively connected to the liquid outlet (solid 2) 410 to receive the material supply of the solid organic matter supply electrode kettle device 4; the liquid inlet 2 (production) 503 is connected to the liquid outlet (main) 105 to receive the reaction product from the high-pressure main reaction electrode kettle device 1.

[0060] The autoclave reaction chamber 7 of the present invention is cylindrical, with a diameter of 10-50 cm and a thickness of more than 5 mm, and is made of one of stainless steel, tungsten and tungsten-molybdenum alloy; the reactor liner 8 is made of insulating inert inorganic materials such as ceramics and corundum; the electrode assembly 9 includes an insulating ceramic plate and an electrode, and the electrode material includes one or more of graphene, carbon, iridium-rhenium and tungsten-rhenium-iridium-potassium alloy.

[0061] like Fig. 9 As shown, the control method of the multiple high-voltage electrode reactor cascade carbon fixation device of the present invention comprises the following steps:

[0062] S1. Determine the target product, prepare the solution and load it into each reactor cavity 7, and apply voltage to each electrode assembly 9 through a plasma power supply. The output voltage of the plasma power supply is 200-5000V, the frequency is 5Hz-1kHz, the output waveform includes one of a sine wave, a square wave and a pulse wave, the output power is 100-20000W, and a stable discharge plasma can be generated after the current stabilizes to 0.05-1A, and the gas and solvent react for a period of time and then enter the subcritical and supercritical state.

[0063] S2, start the reaction, the high-pressure main reaction electrode kettle device 1 delivers the reaction product to the product receiving electrode kettle device 5, and at the same time, the gas supply electrode kettle device 2 supplies most of the gas and part of the water to the high-pressure main reaction electrode kettle device 1, and the solvent supply electrode kettle device 3 and the solid organic matter supply electrode kettle device 4 jointly supply the solvent and a small part of the gas to the high-pressure main reaction electrode kettle device 1. The supply rule is: without affecting the main components of the product, the solid organic matter supply electrode kettle device is the main one, followed by the gas supply electrode kettle device, and finally the solvent supply electrode kettle device; and when the electrode kettle devices exchange solutions with each other, the output amount is equal to the input amount.

[0064] S3. After a period of reaction, the product in each electrode kettle device is taken for composition and content analysis, and compared with the target product, the ratio and composition of the gas and solvent in each electrode kettle device are adjusted by a single factor method, and then the temperature and pressure are adjusted, and finally the power supply parameters are changed to obtain the optimal reaction parameters;

[0065] S4. Obtain the target product and complete the reaction.

[0066] The parameter adjustment steps of each electrode reactor device are as follows: first, change the ratio and content of carbon dioxide, water, nitrogen and organic matter one by one at a certain temperature and pressure, wherein the gas content is adjusted by 0.1MPa each time, and the water and solvent content is adjusted by 0.01% (mol%) each time; then measure and analyze the product composition and content to find the optimal ratio and content of carbon dioxide, water, nitrogen and organic matter; secondly, adjust the temperature and pressure, the temperature is adjusted by 5°C each time, or the pressure is adjusted by 0.1MPa each time, and after each adjustment, it is necessary to analyze the product composition and content to find the optimal temperature and pressure; finally, on the basis of the above, only adjust the power supply parameters (duty cycle, frequency, rising edge, voltage and discharge current, etc.) to finally obtain the optimal parameters.

[0067] The operation method of the feed component 403 is as follows: when the one-way ball valve 403-4 is closed, open the ventilation port 403-1 on the sealing cover 403-2 to ensure that the external air pressure is consistent with the air pressure of the feed bin 403-3, then open the sealing cover 403-2, load plastic into the feed bin 403-3, then close the sealing cover 403-2 and the ventilation port 403-1, slowly open the one-way ball valve 403-4 to make the air pressure in the feed bin 403-3 and the reactor cavity 7 of the solid organic matter replenishment electrode kettle device 4 consistent, and then open the bottom outlet of the feed bin 403-3 to allow the plastic to enter the reactor cavity 7 from the one-way ball valve 403-4 channel.

[0068] In a specific embodiment, the reaction vessel chamber 7 of each electrode reactor device is 2500 ml.

[0069] The high-pressure main reaction electrode kettle device 1 is filled with 411.239 ml of water and 411.23 ml of formaldehyde, and 11 MPa of carbon dioxide is introduced. The liquid phase product is analyzed at 378°C and 32.1 MPa, and the molar ratio of C, H and O is 1:3.8:2.4. The main components include formic acid, formaldehyde, methanol, water and carbon dioxide, among which the formic acid content is 14.15% (mol%), the water content is (34.65%), the methanol content is 8.69% (mol%), the formaldehyde content is 31.07% (mol%), the acetic acid content is 3.35% (mol%), the ethanol content is 5.54% (mol%) and the acetaldehyde content is 2.25% (mol%). When the high-voltage main reaction electrode kettle device 1 receives the supply from the gas supply electrode kettle device 2 at a flow rate of 3.87 m / s, receives the supply from the solvent supply electrode kettle device 3 at a flow rate of 0.39 m / s, receives the supply from the solid organic matter supply electrode kettle device 4 at a flow rate of 0.53 m / s, and outputs the product to the product receiving electrode kettle device 5 at a flow rate of 3.87 m / s, the C, H, and O molar ratio of the output product is 1:2.7:2.1, and the main components include 20.51% (mol%) formic acid, (30.32%) water, 19.42% (mol%) formaldehyde, 11.46% (mol%) acetic acid, 9.07% (mol%) ethanol and 8.81 (mol%) acetaldehyde.

[0070] The gas chamber 201 of the gas supply electrode kettle device 2 is filled with 822.46 ml of water and 22 MPa of carbon dioxide. It is heated to a temperature of 380.2°C and a pressure of 40.2 MPa by discharge plasma, and then the pressure is fine-tuned to 40.3 MPa through power supply parameters. At this time, carbon dioxide and water are injected into the gas chamber 201 at flow rates of 3.23 m / s and 0.16 m / s respectively; the gas chamber 202 contains 822.46 ml of water and 22 MPa of carbon dioxide. When the conditions in the kettle reach 380.2°C and 40.2 MPa, it begins to receive the products of the gas chamber 201 at a flow rate of 1.27 m / s, and at the same time outputs the products to the high-voltage main reaction electrode kettle device 1 at a flow rate of 3.87 m / s. The solution compositions of gas chamber 1 201 and gas chamber 202 are substantially the same. After analyzing the liquid products, it is known that the molar ratio of C, H, and O is 1:3.2:2.1. The main components include 5.25% (mol%) formic acid, (84.35%) water, 3.33% (mol%) methanol, 1.36% (mol%) formaldehyde, 1.85% (mol%) acetic acid, 2.33% (mol%) ethanol, and 1.22% (mol%) acetaldehyde, so C needs to be supplemented.

[0071] The solid chamber 1 401 and the solid chamber 2 402 of the solid organic matter supply electrode kettle device 4 are both filled with 611.23 ml of ethanol, 211.23 ml of water and 12.4 MPa of carbon dioxide. When the conditions in the solid chamber 1 401 and the solid chamber 2 402 reach 395.4°C and 38.6 MPa, polyethylene plastic powder is added to the solid chamber 1 401 at a rate of 0.2 g / min, and the product is output to the solid chamber 2 402 at a flow rate of 0.53 m / s, and the solid chamber 2 402 also outputs the product to the high-voltage main reaction electrode kettle device 1 at a flow rate of 0.53 m / s. During this period, the formic acid content in the solid chamber 401 is 10.06% (mol%), methanol is 7.44% (mol%), formaldehyde is 9.12% (mol%), acetic acid is 12.58% (mol%), ethanol is 20.32% (mol%), and 4.07% (mol%) acetaldehyde. In addition, there are other products such as propionic acid, propanol and isopropanol; while the output products of the solid chamber 402 are (24.65%) water, 20.78% (mol%) formic acid, 5.96% (mol%) methanol, 11.57% (mol%) formaldehyde, 10.65% (mol%) acetic acid, 15.48% (mol%) ethanol and 8.78% (mol%) acetaldehyde. In addition, there are other products such as propionic acid, propanol and isopropanol, so C needs to be supplemented.

[0072] The solvent supply electrode kettle device 3 is filled with 700.00ml ethanol and 111.23ml water, and 5.4MPa carbon dioxide is introduced. When the conditions in the kettle reach 385.4℃ and 41.4MPa, it starts to output products to the high-pressure main reaction electrode kettle device 1 at a flow rate of 1.21m / s. The output products are (10.10%) water, 19.36% (mol%) formic acid, 7.57% (mol%) methanol, 12.32% (mol%) formaldehyde, 20.33% (mol%) acetic acid, 16.48% (mol%) ethanol and 11.23% (mol%) acetaldehyde. In addition, there are other products such as propionic acid, propanol and isopropanol.

[0073] The product receiving electrode kettle device 5 is filled with the same solution as the high-pressure main reaction electrode kettle device 1, and the solvent supply electrode kettle device 3 and the solid organic matter supply electrode kettle device 4 inject the product into the product receiving electrode kettle device 5 at a flow rate of 1.01s / m and 1.77m / s respectively. After adjusting the conditions in the kettle of the product receiving electrode kettle device 5 to 344°C and 26MPa, the final product is output at a flow rate of 4.13m / s. At this time, the molar ratio of C, H, and O in the final product is 1:2.6:2.1, mainly formic acid, formaldehyde, methanol, water, and carbon dioxide, among which the formic acid content is 21.01% (mol%), the water content is (31.32%), the methanol is 8.41% (mol%), the formaldehyde is 11.03% (mol%), the acetic acid is 10.84% ​​(mol%), the ethanol is 10.11% (mol%), and the acetaldehyde is 7.68% (mol%).

[0074] In another specific embodiment, the reaction vessel chamber 7 of each electrode reactor device is 2500 ml.

[0075] The high-pressure main reaction electrode kettle device 1 is filled with 411.23 ml of water and 411.23 ml of methanol, and the pH is adjusted to 12 with NaOH, and then 11 MPa of ammonia is introduced. When the conditions in the kettle are 378°C and 34.8 MPa, analysis of the liquid phase products shows that the molar ratio of C, H, and O is 1:4.2:2.1, mainly composed of methylamine, methanol, formaldehyde, urea, water and carbon dioxide, including 10.15% (mol%), the water content is (39.45%) methylamine, 32.11% (mol%) methanol, 7.85% (mol%) formaldehyde, 4.62% (mol%) urea, 1.21% (mol%) acetic acid, 2.39% (mol%) ethanol and 2.21% (mol%) acetaldehyde. When the high-pressure main reaction electrode kettle device 1 receives the supply from the gas supply electrode kettle device 2 at a flow rate of 0.82 m / s, receives the supply from the solvent supply electrode kettle device 3 at a flow rate of 0.42 m / s, receives the supply from the solid organic matter supply electrode kettle device 4 at a flow rate of 0.56 m / s, and outputs the product to the product receiving electrode kettle device 5 at a flow rate of 3.77 m / s, the molar ratio of C, H, O, and N in the output product is 1:4.3:2.0:0.7.

[0076] The gas chamber 201 of the gas supply electrode kettle device 2 is filled with 822.46 ml of water and 11 MPa of carbon dioxide. The ammonia is further pressurized from 11 MPa to 22 MPa, and is heated to a temperature of 384.6°C and a pressure of 42.1 MPa by using discharge plasma. The pressure is then fine-tuned to 42.0 MPa by power supply parameters. At this time, ammonia, carbon dioxide and water are injected into the gas chamber 201 at flow rates of 2.65 m / s, 2.65 m / s and 0.16 m / s respectively; the gas chamber 202 kettle contains 822.46 ml of water, 11 MPa of carbon dioxide and 11 MPa of ammonia. When the conditions in the kettle reach 384.5°C and 42.0 MPa, the product of the gas chamber 201 is received at a flow rate of 1.04 m / s, and the product is output to the high-voltage main reaction electrode kettle device 1 at a flow rate of 1.04 m / s. The solution composition of gas chamber 1 201 and gas chamber 2 202 is basically the same. After analyzing the liquid phase products, it can be seen that the molar ratio of C, H, O, and N is 1:3.2:2.1:0.3, and it is mainly composed of methylamine, methanol, formaldehyde, water and carbon dioxide, including 5.14% (mol%) methylamine, (84.78%) water, 3.82% (mol%) methanol, 1.91% (mol%) formaldehyde, 2.03% (mol%) urea, 0.36% (mol%) acetic acid, 1.12% (mol%) ethanol and 0.82% (mol%) acetaldehyde, so N and C need to be supplemented.

[0077] The solid chamber 1 401 and the solid chamber 2 402 of the solid organic matter replenishing electrode kettle device 4 are both filled with 611.23 ml of ethanol and 211.23 ml of water, and NaOH is added to adjust the pH to 12, and the ammonia is pressurized to 12.4 MPa. When the conditions in the solid chamber 1 401 and the solid chamber 2 402 reach 395.4°C and 41.7 MPa, the pressure is fine-tuned to 41.8 MPa through the power supply parameters, and urea-formaldehyde resin powder is added to the solid chamber 1 401 at a rate of 0.2 g / min. At the same time, the product is output to the solid chamber 2 402 at a flow rate of 0.37 m / s, and the solid chamber 2 402 outputs the product to the high-pressure main reaction electrode kettle device 1 at a flow rate of 0.56 m / s. During this period, the methylamine content in the solid chamber 1 401 is 14.22% (mol%), the water content is (17.25%), the methanol is 38.89% (mol%), the formaldehyde is 13.92% (mol%), the urea is 6.73% (mol%), the acetic acid is 1.91% (mol%), the ethanol is 4.08% (mol%), and the acetaldehyde is 2.98% (mol%). In addition, there are a small amount of amino acids, etc.; the output products of the solid chamber 2 402 are 15.11% (mol%) methylamine, (17.24%) water, 38.81% (mol%) methanol, 12.91% (mol%) formaldehyde, 6.94% (mol%) urea, 1.97% (mol%) acetic acid, 4.07% (mol%) ethanol and 2.93% (mol%) acetaldehyde. In addition, there are a small amount of amino acids, etc., so N and C need to be supplemented.

[0078] The solvent supply electrode kettle device 3 is filled with 700.00ml methanol and 111.23ml water, and NaOH is added to adjust the pH to 12. At the same time, the ammonia gas is pressurized to 12.4MPa. When the conditions in the kettle reach 393.5℃ and 43.6MPa, the product is output to the high-pressure main reaction electrode kettle device 1 at a flow rate of 0.91m / s. The output products are 8.58% (mol%) methylamine, (18.24%) water, 44.21% (mol%) methanol, 14.84% (mol%) formaldehyde, 4.01% (mol%) urea, 1.7% (mol%) acetic acid, 4.82% (mol%) ethanol and 3.57% (mol%) acetaldehyde. In addition, there are a small amount of amino acids, etc., so N and C need to be supplemented.

[0079] The product receiving electrode kettle device 5 is filled with the same solution as the high-pressure main reaction electrode kettle device 1. The solvent supply electrode kettle device 3 and the solid organic matter supply electrode kettle device 4 inject products into the product receiving electrode kettle device 5 at flow rates of 1.01s / m and 1.77m / s respectively. After adjusting the conditions in the product receiving electrode kettle device 5 to 344℃ and 26MPa, the final product is output at a flow rate of 4.78m / s. At this time, the molar ratio of C, H, O, and N in the final product is 1:2.6:2.1:1.7, mainly composed of methylamine, formaldehyde, methanol, water, and carbon dioxide, among which the methylamine content is 13.95% (mol%), the water content is (30.72%), the methanol content is 32.14% (mol%), the formaldehyde content is 9.67% (mol%), the urea content is 6.64% (mol%), the acetic acid content is 1.34% (mol%), the ethanol content is 2.64% (mol%), and the acetaldehyde content is 2.88% (mol%).

[0080] The above describes the specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A device for cascading carbon fixation of multiple high-voltage electrode reactors, characterized in that: include: High-pressure main reaction electrode kettle device, gas supply electrode kettle device, solvent supply electrode kettle device, solid organic matter supply electrode kettle device and product receiving electrode kettle device; The gas supply electrode kettle device, the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device are respectively connected to the high-voltage main reaction electrode kettle device, and the supply material is transported to the high-voltage main reaction electrode kettle device through each of the supply electrode kettle devices; The high-pressure main reaction electrode kettle device, the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device are respectively connected to the product receiving electrode kettle device, and the product and supply material after the reaction of the high-pressure main reaction electrode kettle device are transported to the product receiving electrode kettle device.

2. The device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 1, characterized in that: The electrode kettle device comprises an external insulation layer and a reactor cavity; the reactor cavity comprises a reactor liner, an electrode assembly, an air inlet, an exhaust port, a liquid inlet, a liquid outlet, a safety valve, a pressure sensor and a temperature sensor.

3. The device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 1 or 2, characterized in that: The gas supply electrode kettle device comprises a gas chamber 1 and a gas chamber 2, wherein the gas chamber 1 and the gas chamber 2 are independent electrode kettle devices; the gas chamber 1 and the gas chamber 2 are connected via an inter-chamber liquid transfer channel I.

4. The device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 1 or 2, characterized in that: The solid organic matter replenishing electrode kettle device comprises a solid organic matter chamber 1 and a solid organic matter chamber 2, wherein the solid organic matter chamber 1 and the solid organic matter chamber 2 are independent electrode kettle devices; the solid organic matter chamber 1 and the solid organic matter chamber 2 are connected via an inter-chamber transfer channel II; the solid organic matter chamber 1 is also provided with a feed assembly, wherein a ventilation port, a sealing cover, a feed bin and a one-way ball valve are sequentially arranged in the feed assembly from top to bottom.

5. A control method for a device for cascading carbon fixation of multiple high-voltage electrode reactors as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Determine the target product, prepare a solution and load it into each of the reaction kettle cavities, and apply voltage to each of the electrode assemblies through a plasma power supply; S2, start the reaction, the high-pressure main reaction electrode kettle device delivers the reaction product to the product receiving electrode kettle device, and at the same time the gas supply electrode kettle device supplies most of the gas and part of the water to the high-pressure main reaction electrode kettle device, and the solvent supply electrode kettle device and the solid organic matter supply electrode kettle device jointly supply the solvent and a small part of the gas to the high-pressure main reaction electrode kettle device; S3. After a period of reaction, the product in each of the electrode kettle devices is taken for component and content analysis, and compared with the target product, the ratio and composition of the gas and solvent in each of the electrode kettle devices are adjusted by a single factor method, and then the temperature and pressure are adjusted, and finally the power supply parameters are changed to obtain the optimal parameters; S4. Obtain the target product and complete the reaction.

6. The control method of the device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 5, characterized in that: In S1, the voltage applied by the plasma power supply is 200-5000V, the frequency is 5Hz-1kHz, the output waveform includes one of a sine wave, a square wave and a pulse wave, and the output power is 100-20000W.

7. The control method of the device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 5, characterized in that: In S2, the replenishment principle of each replenishment electrode kettle device is: under the premise of not affecting the main components of the product, the solid organic matter replenishment electrode kettle device is mainly used, followed by the gas replenishment electrode kettle device, and finally the solvent replenishment electrode kettle device.

8. The control method of the device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 5, characterized in that: In S2, when the electrode reactor devices exchange solutions with each other, the output amount is equal to the input amount.

9. The control method of the device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 8, characterized in that: The rate of solution delivery satisfies the Navier-Stokes equations: ρ is density, u is flow velocity, t is time, is the Laplace operator, p is the pressure, μ is the viscosity coefficient, and g is the gravitational acceleration.

10. The control method of the device for cascading carbon fixation of multiple high-voltage electrode reactors according to claim 5, characterized in that: In S3, each time the parameters are adjusted, the product needs to be analyzed and tested, and compared with the target product to obtain the optimal reaction parameters.

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