Membrane-free electro-catalysis continuous reaction mechanism and PET waste plastic upgrading and reconstruction coupling temperature control hydrogen production device

Abstract

The utility model relates to a membrane-free electro-catalysis continuous reaction mechanism and PET waste plastic upgrading reconstruction coupling temperature control hydrogen production device, the device comprises a raw material mechanism, a continuous reaction mechanism, a temperature control mechanism and a hydrogen transportation mechanism, the raw material mechanism comprises an electrolyte storage tank and a pump, and the continuous reaction mechanism comprises a feed port, a first discharge port and a second discharge port; the at least one electrode unit is connected with a direct-current power supply, the temperature control mechanism comprises a temperature control module and a heating sheet, and the hydrogen transportation mechanism comprises a water-gas separator and a pump; according to the device, the reaction temperature is controlled through the heating plate, electrolyte in the raw material mechanism is upgraded through a catalyst electrode of the electrode unit to be reconstructed into a high-value-added product, meanwhile, hydrogen is generated, the generated hydrogen is collected through the hydrogen conveying mechanism, the high-value-added product is recycled by treating the electrolyte after reaction, and the hydrogen is recycled. The device can enlarge the reaction system, control the temperature, improve the economic benefit, realize large-current long-time stable operation, reduce the pollution of PET waste plastics and realize high-value recovery of resources.

Description

Technical Field

[0001] The utility model relates to the technical field of organic solid waste treatment and resource utilization, in particular to a membrane-free electrocatalytic continuous reaction mechanism and a PET waste plastic upgrading and recycling coupled temperature-controlled hydrogen production device composed of the membrane-free electrocatalytic continuous reaction mechanism. Background Technique

[0002] About 70 million tons of PET plastics are produced globally every year, accounting for about 13% of the total plastic production, and it is growing at a rate of 4.5% per year. It is widely used in industries such as beverage packaging, food packaging, and textiles. Due to the durability and decomposition resistance of PET plastics, it takes about 16 - 48 years for waste PET plastics to be completely degraded in nature. Coupled with the large usage volume, short usage cycle, and improper post-treatment, it has caused serious environmental pollution and resource waste. Therefore, realizing the upgrading and recycling of PET waste plastics has important value both from the perspective of environmental protection and resource recycling.

[0003] Electrocatalysis is a process that, under the drive of an external electric field, reduces the reaction activation energy through the electron interaction between the catalyst and electrolyte molecules, thereby accelerating the molecular transformation. Among them, an oxidation reaction occurs at the anode, and a reduction reaction occurs at the cathode. This technology was first used by the Duan Haohong team at Tsinghua University in 2021 in the field of upgrading and recycling high-value chemicals from PET waste plastics, providing a new way to solve the problems of waste plastic pollution and resource utilization (Nat. Commun. 2021, 12, 4679). Recently, the Chen Yong team at the University of Chinese Academy of Sciences (Chem. Commun. 2021, 57, 12595; Angew. Chem. Int. Edit. 2023, 62, e202300094.), and the Zhao Yixin team at Shanghai Jiao Tong University (J. Phys. Chem. Lett. 2022, 13, 622.) obtained high-value chemicals such as glycolic acid, carbonate, and formate and coupled cathode hydrogen production H 2 through catalyst structure design and different reaction paths. It is worth mentioning that this process can not only synthesize high-value chemicals, but also reduce the energy consumption of electrolytic water hydrogen production H 2 significantly by replacing the slow anodic oxygen evolution reaction (OER) in the electrolytic water process.

[0004] However, the existing reported electrocatalytic PET waste plastic upgrading and recycling coupled electrolytic water hydrogen production processes are generally carried out under (1) an intermittent three-electrode system, but the reaction substrate concentration is low and the reaction volume is small, making it difficult to be applied in practice; (2) in a reaction device with a proton or anion exchange membrane added, but the exchange membrane cost is high, and the electrolyte will react with CO in the air 2The reaction forms carbonates that are insoluble in water under alkaline conditions, resulting in the clogging of the diaphragm layer, hindering the normal progress of the reaction, and greatly reducing the performance of the electrolytic cell.

[0005] The Chinese patent document (publication number CN218539843U) discloses a device for electrocatalytic oxidation of biomass derivatives. Although it realizes the continuous electrocatalytic oxidation reaction function of biomass derivatives, it cannot meet the high-temperature operation requirements of 80-90°C in actual industrial conditions, and at the same time, it cannot carry out the coupled hydrogen production reaction.

[0006] The Chinese patent document (publication number CN114959749A) discloses a method for electrocatalytic glycol or electrocatalytic reforming of waste plastic PET to prepare glycolate. The flow electrolytic cell used has a simple structure, a small effective area of the catalyst electrode, and cannot meet the high-temperature operation requirements in actual industrial conditions.

[0007] Therefore, to realize the industrial application of the electrocatalytic PET waste plastic upgrading and recycling coupled hydrogen production process, it is necessary to expand the reaction system, increase the reaction rate, reduce the equipment cost, reduce the generation of non-Faradaic products, improve the product selectivity, and achieve stable high-yield production with large current for a long time. Summary of the Invention

[0008] In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present utility model is to provide a membrane-free electrocatalytic continuous reaction mechanism and a PET waste plastic upgrading and recycling coupled temperature-controlled hydrogen production device. By adding a temperature control module, removing the exchange membrane, and using a special catalyst electrode to control the reaction conditions, it solves the problems of the current electrooxidation coupled hydrogen production device such as inability to continuously produce, low reaction substrate concentration, small reaction volume, high cost and easy clogging of the exchange membrane, and low target product selectivity, and promotes the industrial application of the electrocatalytic PET waste plastic upgrading and recycling high-value-added chemical coupled hydrogen production process.

[0009] In order to achieve the above purpose, the technical solution adopted by the present utility model is:

[0010] The membrane-free electrocatalytic continuous reaction mechanism includes a housing. The two ends of the housing are respectively provided with a feed-side shell plate and a discharge-side shell plate. A feed inlet 21 is provided at the lower end of the feed-side shell plate, a first discharge outlet 22 is provided at the upper end of the discharge-side shell plate, a second discharge outlet 23 is provided at the lower end of the discharge-side shell plate, and at least one group of electrode units 24 is arranged between the feed-side shell plate and the discharge-side shell plate. Each group of electrode units 24 is connected to a DC power supply.

[0011] The first discharge outlet 22 and the second discharge outlet 23 are arranged diagonally on the discharge-side shell plate.

[0012] The electrode unit 24 includes an anode current collector plate 241, an anode 242, a first gasket 243, a cathode 244, and a cathode current collector plate 245 that are stacked in sequence. The anode current collector plate 241 is close to the feed-side housing plate, and the cathode current collector plate 245 is close to the discharge-side housing plate.

[0013] A square through-hole is opened in the lower part of the anode current collector plate 241 as an anode mixing chamber 2411, and a square through-hole is opened in the upper part as an anode discharge chamber 2412. In the middle section of the anode current collector plate 241 between the anode mixing chamber 2411 and the anode discharge chamber 2412, an S-shaped coiled anode liquid flow channel 2413 is formed. The liquid inlet and outlet of the anode liquid flow channel 2413 are arranged diagonally and are respectively communicated with the anode mixing chamber 2411 and the anode discharge chamber 2412.

[0014] A square through-hole is opened in the lower part of the cathode current collector plate 245 as a cathode mixing chamber 2451, and a square through-hole is opened in the upper part as a cathode discharge chamber 2452. In the middle section of the cathode current collector plate 245 between the cathode mixing chamber 2451 and the cathode discharge chamber 2452, an S-shaped coiled cathode liquid flow channel 2453 is formed. The liquid inlet and outlet of the cathode liquid flow channel 2453 are arranged diagonally and are respectively communicated with the cathode mixing chamber 2451 and the cathode discharge chamber 2452. And when only one set of electrode units 24 is provided or for the electrode unit 24 closest to the discharge-side housing plate among multiple sets of electrode units 24, only a square through-hole is opened in the upper part of the cathode current collector plate 245 as the cathode discharge chamber 2452.

[0015] The anode 242 includes an anode conductive substrate, and an anode catalyst is loaded on the anode conductive substrate.

[0016] The cathode 244 includes a cathode conductive substrate, and a cathode catalyst is loaded on the cathode conductive substrate.

[0017] The first gasket 243 is successively provided with three square through-holes from bottom to top as a mixing chamber 2431, a reaction chamber 2432, and a discharge chamber 2433. The anode 242 and the cathode 244 are covered on both sides of the reaction chamber 2432.

[0018] The feed port 21 is successively communicated with the anode mixing chamber 2411, the mixing chamber 2431, and the cathode mixing chamber 2451.

[0019] The anode discharge chamber 2412 is successively communicated with the discharge chamber 2433, the cathode discharge chamber 2452, and the first discharge port 22.

[0020] The anode liquid flow channel 2413 is successively communicated with the reaction chamber 2432 and the cathode liquid flow channel 2453.

[0021] A raised anode connection board 2414 is provided at the top of the anode current collector plate 241, and a raised cathode connection board 2454 is provided at the top of the cathode current collector plate 245. The anode connection board 2414 is connected to the positive pole of the DC power supply, and the cathode connection board 2454 is connected to the negative pole of the DC power supply, and the anode connection board 2414 and the cathode connection board 2454 are arranged alternately.

[0022] A third gasket 247 is provided between the anode current collector plate 241 and the feed side housing plate.

[0023] A layer of fourth gasket 248 is further provided between the anode 242 and the first gasket 243.

[0024] A layer of fifth gasket 249 is further provided between the cathode 244 and the first gasket 243.

[0025] The structures of the third gasket 247, the fourth gasket 248 and the fifth gasket 249 are the same as those of the first gasket 243.

[0026] A second gasket 246 is provided between the cathode current collector plate 245 and the discharge side housing plate. The second gasket 246 is provided with a square through hole as the second discharge cavity 2461, and the thickness is greater than that of the first gasket 243.

[0027] The second discharge cavity 2461 is respectively communicated with the cathode discharge cavity 2452, the first discharge port 22 and the second discharge port 23.

[0028] When there are multiple groups of the electrode units 24, a first gasket 243 is provided between adjacent electrode units 24.

[0029] The materials of the feed side housing plate, the discharge side housing plate, the anode current collector plate 241 and the cathode current collector plate 245 are nickel, iron or titanium.

[0030] The thicknesses of the first gasket 243, the third gasket 247, the fourth gasket 248 and the fifth gasket 249 are all 0.02 cm to 0.5 cm, and the materials are all polytetrafluoroethylene, silica gel, fluororubber, polyether ether ketone or rubber.

[0031] The distance between the anode current collector plate 241 and the cathode current collector plate 245 of adjacent electrode units 24 is 0.02 cm to 1 cm.

[0032] The area of the anode 242 or the cathode 244 is not less than 50 cm 2 .

[0033] The PET waste plastic upgrading and recycling coupled temperature-controlled hydrogen production device based on the membrane-free electrocatalytic continuous reaction mechanism includes:

[0034] A raw material mechanism 1 for providing raw materials required for hydrogen production;

[0035] A continuous reaction mechanism 2 for continuously reacting to the raw materials provided by the raw material mechanism 1;

[0036] A temperature control mechanism 3 for controlling the temperature of the continuous reaction mechanism 2;

[0037] A hydrogen transportation mechanism 4 for collecting the hydrogen prepared after the reaction of the continuous reaction mechanism 2 and recycling the waste materials after the reaction.

[0038] The raw material mechanism 1 includes an electrolyte storage tank 11, and an electrolyte feeding pump 12 is arranged at the discharge port of the electrolyte storage tank 11. The electrolyte feeding pump 12 is communicated with the feeding port 21 of the continuous reaction mechanism 2;

[0039] The temperature control mechanism 3 includes a temperature control module 31, and the temperature control module 31 is controllably connected to a plurality of heating sheets 32. The heating sheets 32 cover the feeding side shell plate and the discharging side shell plate of the continuous reaction mechanism 2;

[0040] The hydrogen transportation mechanism 4 includes a water-gas separator 41, and a water pump 42 is arranged at the liquid outlet hole of the water-gas separator 41. The water pump 42 is communicated with the electrolyte storage tank 11 of the raw material mechanism 1;

[0041] The first discharge port 22 of the continuous reaction mechanism 2 is communicated with the water-gas separator 41 of the hydrogen transportation mechanism 4.

[0042] Compared with the prior art, the beneficial effects of the present utility model are as follows:

[0043] 1. The present utility model uses the method of setting gaskets to replace the proton membrane, realizing the upgrading and recycling of PET waste plastics into high-value-added chemicals without a membrane, and having the effects of reducing equipment costs on the premise of ensuring equipment performance and quickly converting reaction substrates into target products.

[0044] 2. The present utility model effectively improves the reaction rate by introducing a temperature control module, and has the effect of reducing the generation of non-Faraday products.

[0045] 3. The present utility model expands the reaction system by increasing the number of stacks, and has the effect of stably operating for a long time under large current conditions.

[0046] In summary, the present utility model has the characteristics of high product selectivity, high yield, continuous production, and good stability. Description of the Drawings

[0047] Figure 1 It is a schematic structural diagram of the PET waste plastic upgrading and recycling coupled temperature control hydrogen production device of the present utility model.

[0048] Figure 2 It is a schematic structural diagram of the continuous reaction mechanism 2 of the present utility model.

[0049] Figure 3 This is a schematic structural view of the continuous reaction mechanism 2 of the present utility model when only one set is provided or when multiple sets are provided and the set closest to the discharge side shell plate is considered.

[0050] Figure 4 This is a schematic structural view of three sets of continuous reaction mechanisms 2 according to an embodiment of the present utility model.

[0051] Figure 5 This is a physical diagram of the present utility model.

[0052] In the figure, 1. Raw material mechanism; 11. Electrolyte storage tank; 12. Electrolyte feeding pump; 2. Continuous reaction mechanism; 21. Feed inlet; 22. First discharge port; 23. Second discharge port; 24. Electrode unit; 241. Anode current collector plate; 2411. Anode mixing chamber; 2412. Anode discharge chamber; 2413. Anode liquid flow channel; 2414. Anode connection board; 242. Anode; 243. First gasket; 2431. Mixing chamber; 2432. Reaction chamber; 2433. Discharge chamber; 244. Cathode; 245. Cathode current collector plate; 2451. Cathode mixing chamber; 2452. Cathode discharge chamber; 2453. Cathode liquid flow channel; 2454. Cathode connection board; 246. Second gasket; 2461. Second discharge chamber; 247. Third gasket; 248. Fourth gasket; 249. Fifth gasket; 3. Temperature control mechanism; 31. Temperature control module; 32. Heating sheet; 4. Hydrogen transportation mechanism; 41. Water-vapor separator; 42. Water pump. Detailed implementation manners

[0053] The structural principle and working principle of the present utility model will be described in detail below with reference to the accompanying drawings.

[0054] The membrane-free electrocatalytic continuous reaction mechanism 2 includes a housing. The two ends of the housing are respectively provided with a feed side shell plate and a discharge side shell plate. A feed inlet 21 is provided at the lower end of the feed side shell plate made of nickel, and a first discharge port 22 is provided at the upper end of the discharge side shell plate made of nickel and a second discharge port 23 is provided at the lower end of the discharge side shell plate. Three sets of electrode units 24 are arranged between the feed side shell plate and the discharge side shell plate, as Figure 4 shown, and are fixedly connected by bolts. Each set of electrode units 24 is connected to a DC power supply.

[0055] As Figure 2 、 Figure 3 shown, the first discharge port 22 and the second discharge port 23 are arranged diagonally on the discharge side shell plate.

[0056] As Figure 2As shown, the electrode unit 24 includes an anode current collector plate 241 made of nickel, an anode 242, a first gasket 243, a cathode 244, and a cathode current collector plate 245 made of nickel, which are stacked in sequence. The anode current collector plate 241 is close to the feed side shell plate, and the cathode current collector plate 245 is close to the discharge side shell plate.

[0057] As Figure 2 shown, a square through-hole is opened in the lower part of the anode current collector plate 241 as an anode mixing chamber 2411, and a square through-hole is opened in the upper part as an anode discharge chamber 2412. In the middle section of the anode current collector plate 241 between the anode mixing chamber 2411 and the anode discharge chamber 2412, an S-shaped coiled anode liquid flow channel 2413 is formed. The liquid inlet and outlet of the anode liquid flow channel 2413 are arranged diagonally and are respectively communicated with the anode mixing chamber 2411 and the anode discharge chamber 2412.

[0058] As Figure 2 shown, a square through-hole is opened in the lower part of the cathode current collector plate 245 as a cathode mixing chamber 2451, and a square through-hole is opened in the upper part as a cathode discharge chamber 2452. In the middle section of the cathode current collector plate 245 between the cathode mixing chamber 2451 and the cathode discharge chamber 2452, an S-shaped coiled cathode liquid flow channel 2453 is formed. The liquid inlet and outlet of the cathode liquid flow channel 2453 are arranged diagonally and are respectively communicated with the cathode mixing chamber 2451 and the cathode discharge chamber 2452, as Figure 3 、 Figure 4 shown, and when only one set of electrode units 24 is provided or among multiple sets of electrode units 24, for the cathode current collector plate 245 of the electrode unit 24 closest to the discharge side shell plate, only a square through-hole is opened in the upper part as the cathode discharge chamber 2452.

[0059] As Figure 2 、 Figure 3 shown, the anode 242 includes an anode conductive substrate, on which an anode catalyst is loaded, with an area of 50 cm 2 .

[0060] As Figure 2 、 Figure 3 shown, the cathode 244 includes a cathode conductive substrate, on which a cathode catalyst is loaded, with an area of 50 cm 2 .

[0061] The anode catalyst electrode 242 and the cathode catalyst electrode 244 control the reaction conditions to upgrade and recycle waste plastic PET into high-value-added chemicals.

[0062] As Figure 2 、 Figure 3As shown, the first gasket 243 is made of rubber with a thickness of 0.5 cm, and is successively provided with three square through holes from bottom to top as a mixing chamber 2431, a reaction chamber 2432, and a discharge chamber 2433. The two sides of the reaction chamber 2432 are covered with an anode 242 and a cathode 244.

[0063] As Figure 2 shown, the feed inlet 21 is successively communicated with an anode mixing chamber 2411, a mixing chamber 2431, and a cathode mixing chamber 2451.

[0064] As Figure 2 、 Figure 3 shown, the anode discharge chamber 2412 is successively communicated with a discharge chamber 2433, a cathode discharge chamber 2452, and a first discharge port 22.

[0065] As Figure 2 shown, the anode liquid flow channel 2413 is successively communicated with a reaction chamber 2432 and a cathode liquid flow channel 2453.

[0066] As Figure 1 、 Figure 2 、 Figure 3 shown, a raised anode connection board 2414 is provided at the top of the anode current collector plate 241, and a raised cathode connection board 2454 is provided at the top of the cathode current collector plate 245. The anode connection board 2414 is connected to the positive pole of a DC power supply, and the cathode connection board 2454 is connected to the negative pole of the DC power supply, and the anode connection board 2414 and the cathode connection board 2454 are arranged in an interleaved manner.

[0067] As Figure 2 、 Figure 3 shown, a third gasket 247 is provided between the anode current collector plate 241 and the feed side shell plate.

[0068] As Figure 2 、 Figure 3 shown, a layer of fourth gasket 248 is further provided between the anode 242 and the first gasket 243.

[0069] As Figure 2 、 Figure 3 shown, a layer of fifth gasket 249 is further provided between the cathode 244 and the first gasket 243.

[0070] As Figure 2 、 Figure 3 shown, the structures of the third gasket (247), the fourth gasket (248), and the fifth gasket (249) are the same as those of the first gasket (243).

[0071] As Figure 2 、 Figure 3As shown, a second gasket 246 is provided between the cathode current collector plate 245 and the discharge side shell plate. The second gasket 246 is provided with a square through hole as the second discharge chamber 2461, and its thickness is greater than that of the first gasket 243. It is used for buffering the mixed liquid of the electrolyte and hydrogen after the reaction. The generated gas is discharged from the first discharge port 22, and the generated electrolyte containing formate is discharged from the second discharge port 23.

[0072] As Figure 2 、 Figure 3 shown, the second discharge chamber 2461 is respectively communicated with the cathode discharge chamber 2452, the first discharge port 22 and the second discharge port 23.

[0073] As Figure 4 shown, a layer of first gasket 243 is provided between the three groups of electrode units 24.

[0074] As Figure 1 、 Figure 5 shown, the PET waste plastic upgrading and recycling coupled temperature-controlled hydrogen production device based on the membrane-free electrocatalytic continuous reaction mechanism includes a raw material mechanism 1 for providing raw materials required for hydrogen production, a membrane-free electrocatalytic continuous reaction mechanism 2 for continuously reacting the raw materials provided by the raw material mechanism 1, a temperature control mechanism 3 for controlling the temperature of the continuous reaction mechanism 2, and a hydrogen transportation mechanism 4 for collecting the hydrogen prepared after the reaction of the continuous reaction mechanism 2 and recycling the waste materials after the reaction;

[0075] As Figure 1 shown, the raw material mechanism 1 includes an electrolyte storage tank 11. An electrolyte feeding pump 12 is provided at the discharge port of the electrolyte storage tank 11. The electrolyte feeding pump 12 is communicated with the feed port 21 of the continuous reaction mechanism 2. The electrolyte in the electrolyte storage tank 11 can be a 1-10M sodium hydroxide or potassium hydroxide solution in which PET waste plastic is dissolved. In this embodiment, the electrolyte in the electrolyte storage tank 11 is a 10M sodium hydroxide solution in which PET waste plastic is dissolved;

[0076] The temperature control mechanism 3 includes a temperature control module 31. The temperature control module 31 is controlled to connect two heating sheets 32. The two heating sheets 32 respectively cover the feed side shell plate and the discharge side shell plate of the continuous reaction mechanism 2;

[0077] The hydrogen transportation mechanism 4 includes a water-gas separator 41 for separating the generated gas. A water pump 42 is provided at the liquid outlet hole of the water-gas separator 41. The water pump 42 is communicated with the electrolyte storage tank 11 of the raw material mechanism 1 to provide the required water source during the separation process;

[0078] The first discharge port 22 of the continuous reaction mechanism 2 is communicated with the water-gas separator 41 of the hydrogen transportation mechanism 4.

[0079] The working principle of the present utility model is:

[0080] Store the electrolyte solution in which PET waste plastics are dissolved in the electrolyte storage tank 11. The electrolyte feed pump 12 feeds the reaction materials into the continuous reaction mechanism 2. Control the temperature required for the reaction through the temperature control mechanism 3. Start the DC power supply to ensure that the anode current collector plate 241 is connected to the positive pole of the DC power supply, and the cathode current collector plate 245 is connected to the negative pole of the DC power supply. Under the control of the temperature control mechanism 3, the continuous reaction mechanism 2 ensures that the reaction temperature is stable within the set temperature range. As the electrocatalytic reaction proceeds, the PET waste plastics will be upgraded and recycled into formate solution, and hydrogen gas will be generated simultaneously. Discharge the generated formate through the second discharge port 23, and the hydrogen gas and a small amount of formate solution enter the hydrogen transportation mechanism 4 through the first discharge port 22. The water-gas separator 41 separates the hydrogen gas and pumps the formate solution into the electrolyte storage tank 11 through the water pump 42 for subsequent further separation and purification.

[0081] Application Example 1

[0082] Apply the present utility model to the electrocatalytic upgrading and recycling of PET waste plastics to couple the production of formate and hydrogen. In this embodiment, the alkaline electrolyte is 1 mol / L potassium hydroxide in which 10 g of PET waste plastics are dissolved.

[0083] In this embodiment, the working areas of both the anode 242 and the cathode 244 are 50 cm 2 , the anode 242 is a palladium electrode material supported by nickel hydroxide (Pd / NiOOH) with a size of 7.1 cm * 7.1 cm, and the cathode 244 is a nickel foam with a size of 7.1 cm * 7.1 cm.

[0084] Stably operate for more than 150 h at a current of 2 A. The single-pass conversion rate of PET is about 85%, and the selectivity of formate is as high as 83%. Compared with the prior art, the single-pass conversion rate of PET is increased by 8%, and the selectivity of formate is increased by 12%.

[0085] Application Example 2

[0086] Apply the present utility model to the electrocatalytic upgrading and recycling of PET waste plastics to couple the production of formate and hydrogen. In this embodiment, the alkaline electrolyte is 5 mol / L potassium hydroxide, and the PET hydrolysis solution and the potassium hydroxide solution are injected into the continuous reaction mechanism at the same flow rate.

[0087] In this embodiment, the working areas of both the anode 242 and the cathode 244 are 50 cm 2 , the anode 242 is a bimetallic layered hydroxide (NiCo-LDH) with a size of 7.1 cm * 7.1 cm, and the cathode 244 is a nickel foam with a size of 7.1 cm * 7.1 cm.

[0088] It can stably operate for more than 70 h at a current of 5 A, the single-pass conversion rate of PET is about 80%, and the formate selectivity reaches 78%. Compared with the prior art, the single-pass conversion rate of PET is increased by 5%, and the formate selectivity is increased by 10%.

Claims

1. A membraneless electrocatalytic continuous reaction mechanism, comprising a shell, wherein both ends of the shell are respectively provided with a feed side shell plate and a discharge side shell plate, wherein: A feed port (21) is provided at the lower end of the feed side shell plate, a first discharge port (22) is provided at the upper end of the discharge side shell plate, a second discharge port (23) is provided at the lower end of the discharge side shell plate, at least one group of electrode units (24) is provided between the feed side shell plate and the discharge side shell plate, and each group of electrode units (24) is connected to a DC power supply; The electrode unit (24) comprises an anode current collecting plate (241), an anode (242), a first gasket (243), a cathode (244) and a cathode current collecting plate (245) which are stacked in sequence, the anode current collecting plate (241) being close to a side of a shell plate on the feeding side, and the cathode current collecting plate (245) being close to a side of a shell plate on the discharging side; The anode current collecting plate (241) has a square through hole at the bottom as an anode mixing chamber (2411), and has a square through hole at the top as an anode discharge chamber (2412); an S-shaped coiled anode liquid flow channel (2413) is formed in the middle section of the anode current collecting plate (241) between the anode mixing chamber (2411) and the anode discharge chamber (2412); a liquid inlet and a liquid outlet of the anode liquid flow channel (2413) are arranged diagonally and are respectively connected to the anode mixing chamber (2411) and the anode discharge chamber (2412); The cathode current collector (245) has a square through hole at the bottom as a cathode mixing chamber (2451), and has a square through hole at the top as a cathode discharge chamber (2452); an S-shaped winding cathode liquid flow channel (2453) is formed in the middle section of the cathode current collector (245) between the cathode mixing chamber (2451) and the cathode discharge chamber (2452); the liquid inlet and the liquid outlet of the cathode liquid flow channel (2453) are arranged diagonally and are respectively connected to the cathode mixing chamber (2451) and the cathode discharge chamber (2452); and when only one group of electrode units (24) is provided or when multiple groups of electrode units (24) are provided, the cathode current collector (245) of the electrode unit (24) closest to the discharge side shell plate has only a square through hole at the top as the cathode discharge chamber (2452); The anode (242) comprises an anode conductive substrate, and an anode catalyst is loaded on the anode conductive substrate; The cathode (244) comprises a cathode conductive substrate, on which a cathode catalyst is supported; The first gasket (243) is provided with three square through holes from bottom to top, serving as a mixing chamber (2431), a reaction chamber (2432) and a discharge chamber (2433), and both sides of the reaction chamber (2432) are covered with an anode (242) and a cathode (244); The feed port (21) is sequentially connected to the anode mixing chamber (2411), the mixing chamber (2431) and the cathode mixing chamber (2451); The anode discharge chamber (2412) is sequentially connected to the discharge chamber (2433), the cathode discharge chamber (2452) and the first discharge port (22); The anode liquid flow channel (2413) is connected to the reaction chamber (2432) and the cathode liquid flow channel (2453) in sequence.

2. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: The first discharge port (22) and the second discharge port (23) are arranged diagonally on the discharge side shell plate.

3. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: The anode current collecting plate (241) is provided with a raised anode terminal plate (2414) at the top, and the cathode current collecting plate (245) is provided with a raised cathode terminal plate (2454) at the top. The anode terminal plate (2414) is connected to the positive pole of the DC power supply, and the cathode terminal plate (2454) is connected to the negative pole of the DC power supply. The anode terminal plate (2414) and the cathode terminal plate (2454) are arranged alternately.

4. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: A third gasket (247) is provided between the anode current collecting plate (241) and the feed side shell plate; A fourth gasket (248) is further disposed between the anode (242) and the first gasket (243); A fifth gasket (249) is further provided between the cathode (244) and the first gasket (243); The structures of the third gasket (247), the fourth gasket (248) and the fifth gasket (249) are the same as those of the first gasket (243); A second gasket (246) is provided between the cathode current collecting plate (245) and the discharge side shell plate, the second gasket (246) is provided with a square through hole as a second discharge cavity (2461), and has a thickness greater than that of the first gasket (243); The second discharge chamber (2461) is respectively connected to the cathode discharge chamber (2452), the first discharge port (22) and the second discharge port (23).

5. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: When there are multiple groups of electrode units (24), a first gasket (243) is provided between adjacent electrode units (24).

6. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: The materials of the feed side shell plate, the discharge side shell plate, the anode current collecting plate (241) and the cathode current collecting plate (245) are all nickel, iron or titanium.

7. The membraneless electrocatalytic continuous reaction mechanism according to claim 1, characterized in that: The thickness of the first gasket (243), the third gasket (247), the fourth gasket (248) and the fifth gasket (249) are all 0.02 cm to 0.5 cm, and the materials are all tetrafluoroethylene, silicone, fluororubber, polyetheretherketone or rubber; The distance between the anode current collecting plate (241) and the cathode current collecting plate (245) of the electrode unit (24) is 0.02 cm to 1 cm; The area of ​​the anode (242) or cathode (244) is not less than 50 cm 2 .

8. A PET waste plastic upcycling coupled with temperature-controlled hydrogen production device without a membrane-free electrocatalytic continuous reaction mechanism, characterized in that: include: A raw material mechanism (1), used for providing raw materials required for hydrogen production; A continuous reaction mechanism (2) according to any one of claims 1 to 7, used for continuously reacting the raw materials provided by the raw material mechanism (1); A temperature control mechanism (3) is used to control the temperature of the continuous reaction mechanism (2); The hydrogen transport mechanism (4) is used to collect the hydrogen produced after the reaction of the continuous reaction mechanism (2) and to recover the waste materials after the reaction.

9. The PET waste plastics upgrading and recycling coupled temperature-controlled hydrogen production device according to claim 8, characterized in that: The raw material mechanism (1) comprises an electrolyte storage tank (11), the discharge port of the electrolyte storage tank (11) is provided with an electrolyte feed pump (12), and the electrolyte feed pump (12) is connected to the feed port (21) of the continuous reaction mechanism (2); The temperature control mechanism (3) comprises a temperature control module (31), the temperature control module (31) controls and connects a plurality of heating plates (32), and the heating plates (32) are covered on the feed side shell plate and the discharge side shell plate of the continuous reaction mechanism (2); The hydrogen transport mechanism (4) comprises a water-gas separator (41), a liquid outlet of the water-gas separator (41) is provided with a water pump (42), and the water pump (42) is connected to the electrolyte storage tank (11) of the raw material mechanism (1); The first discharge port (22) of the continuous reaction mechanism (2) is in communication with the water-gas separator (41) of the hydrogen transport mechanism (4).

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