Plasma-driven biomass and hydrogen-rich raw material synergistic pyrolysis upgrading system and method

Abstract

The invention relates to the technical field of biomass high-valued processing, and particularly discloses a plasma-driven biomass and hydrogen-rich raw material collaborative pyrolysis upgrading system and method, and the plasma-driven biomass and hydrogen-rich raw material collaborative pyrolysis upgrading system comprises a pyrolysis reaction system, a plasma collaborative upgrading reaction system and a condensation system. In the pyrolysis reaction system, a hydrogen-rich raw material pyrolysis reactor and a biomass pyrolysis reactor respectively pyrolyze corresponding raw materials, and a gas-gas / gas-solid synergistic reaction mode is selected through valve switching. The plasma synergetic upgrading reaction system excites plasma through dielectric barrier discharge, and performs online catalytic hydrodeoxygenation on pyrolysis gas to produce a target hydrogenation product. And the condensation system performs gas-liquid separation on the hydrogenation product. According to the present invention, the gas-gas / gas-solid mode is provided, the hydrogen-rich raw material pyrolysis gas and the biomass pyrolysis gas are subjected to the synergistic catalytic hydrogenation reaction under the normal pressure to generate the high value-added hydrocarbon liquid fuel, the good applicability is provided for different types of biomass, and compared with the traditional process, the advantages of high raw material utilization rate, convenient flexible regulation and high safety are provided.

Description

Technical Field

[0001] The present application relates to the technical field of biomass upgrading, and in particular to a plasma-driven biomass and hydrogen-rich raw material co-pyrolysis upgrading system and method. Background Art

[0002] With the increasing global demand for sustainable energy and environmental protection materials, the efficient co-conversion technology of biomass and hydrogen-rich raw materials has become a research hotspot. Biomass (crop straw, wood chips, etc.), as an important renewable resource, the oxygen-containing characteristics of its pyrolysis products lead to technical bottlenecks such as low hydrodeoxygenation efficiency and serious coking during the direct upgrading process. The pyrolysis of hydrogen-rich raw materials (plastics, rubbers, etc.) can produce pyrolysis products with certain value, such as olefins, aromatics, etc. However, when treating the pyrolysis products of hydrogen-rich raw materials alone, the product distribution is complex, the yield of high-quality products is low, and problems such as carbon deposition are easily generated during the pyrolysis process, affecting the stable operation of the pyrolysis equipment. By co-processing biomass and hydrogen-rich raw materials, the hydrogen-rich gas generated by the pyrolysis of hydrogen-rich raw materials can be used as the hydrogen source for the hydrodeoxygenation of the gas-phase volatiles of biomass pyrolysis, reducing the use of additional hydrogen.

[0003] The defects of the current co-conversion technology of biomass and hydrogen-rich raw materials are mainly reflected in: (1) a single reaction mode cannot adapt to the physical property differences of multi-source biomass, resulting in insufficient control accuracy of oxygen-containing components; (2) the hydrogen source distribution strategy is rigid and difficult to cope with the dynamic changes of raw material supply; (3) the process of pre-hydrogenation and deep hydrogenation is split, resulting in low hydrogen energy utilization efficiency. Summary of the Invention

[0004] The inventive concept of the present application is as follows: Using the pyrolysis gas of hydrogen-rich raw materials as an independent hydrogen source directly for the hydro-upgrading of biomass pyrolysis gas (gas-gas mode) can utilize its hydrogen-rich characteristics to reduce the external hydrogen supply demand. However, for high-oxygen-containing biomass (such as straw-like herbaceous raw materials), its deoxygenation efficiency is limited by the insufficient depth of single-stage hydrogenation reaction. And pre-introducing the pyrolysis gas of hydrogen-rich raw materials into the gas-solid co-pyrolysis section of biomass (gas-solid mode) can achieve preliminary deoxygenation in the pyrolysis stage through in-situ hydrogenation, thereby improving the hydrogenation efficiency. However, due to the consumption of some active hydrogen components, a higher amount of hydrogen needs to be supplemented in the subsequent upgrading stage. More importantly, there are significant differences in biomass types: hardwood raw materials (such as pine) have a high lignin content and relatively low oxygen content in pyrolysis gas, which are suitable for direct gas-gas co-hydrogenation; while herbaceous raw materials (such as straw) have a high cellulose / hemicellulose ratio and high oxygen content in pyrolysis gas, and efficient conversion and flexible regulation of multi-source biomass can be achieved only through the flexible selection and combination of pre-hydrogenation in gas-solid mode and deep deoxygenation in gas-gas mode. In addition, there are fluctuations in the supply of hydrogen-rich raw materials in actual production. When raw materials such as plastics are sufficient, the gas-gas mode can give full play to its hydrogen source advantage; while when the supply is insufficient, the gas-solid mode can give priority to ensuring the pretreatment requirements of high-oxygen-containing biomass.

[0005] In view of the deficiencies of the current co - conversion technology of biomass and hydrogen - rich raw materials, the present application provides a plasma - driven co - pyrolysis and upgrading system and method for biomass and hydrogen - rich raw materials.

[0006] The plasma - driven co - pyrolysis and upgrading system for biomass and hydrogen - rich raw materials provided by the present application adopts the following technical solutions: The plasma - driven co - pyrolysis and upgrading system for biomass and hydrogen - rich raw materials includes: A pyrolysis reaction system, including a hydrogen - rich raw material pyrolysis reactor, a biomass pyrolysis reactor, and a valve connected between the two. The hydrogen - rich raw material pyrolysis reactor is connected with a hydrogen - rich raw material pyrolysis gas discharge pipeline. A gas inlet is provided on the biomass pyrolysis reactor. The biomass pyrolysis reactor is connected with a biomass pyrolysis gas discharge pipeline. The valve is used to introduce the hydrogen - rich raw material pyrolysis gas discharged from the hydrogen - rich raw material pyrolysis reactor into the hydrogen - rich raw material pyrolysis gas discharge pipeline or into the biomass pyrolysis reactor through the gas inlet; A plasma - assisted upgrading reaction system, including a co - reactor, which generates plasma by using dielectric barrier discharge technology to perform on - line catalytic hydro - deoxygenation on the pyrolysis gas. The co - reactor is connected to the hydrogen - rich raw material pyrolysis gas discharge pipeline and the biomass pyrolysis gas discharge pipeline; A condensation system, which is used for gas - liquid separation of the hydrogenation products of the plasma - assisted upgrading reaction system.

[0007] The present application realizes the flexible switching between the gas - gas mode and the gas - solid mode by switching and distributing the flow direction of the hydrogen - rich raw material pyrolysis gas through the valve, and is applicable to various reaction systems with different oxygen contents in biomass and different supply amounts of hydrogen - rich raw materials.

[0008] The gas - gas mode is mainly applied to the case where there is sufficient hydrogen - rich raw material. In the gas - gas mode, the valve is closed, and the hydrogen - rich raw material pyrolysis gas enters the co - reactor through the hydrogen - rich raw material pyrolysis gas discharge pipeline, and performs a co - catalytic hydrogenation reaction with the biomass pyrolysis gas entering the co - reactor. The hydrogen - rich components in the hydrogen - rich raw material pyrolysis gas can be excited to generate hydrogen plasma, thereby reducing energy consumption, reducing the use of external hydrogen by the hydrogenation module, and using the hydrogen - rich raw material pyrolysis gas as an effective hydrogen source.

[0009] The gas - solid mode is mainly applied to the case where the amount of hydrogen - rich raw material is relatively small. In the gas - solid mode, the valve is opened, and the hydrogen - rich raw material pyrolysis gas enters the biomass pyrolysis reactor through the gas inlet, and co - pyrolyzes with the biomass solid. Moreover, the hydrogen - rich raw material pyrolysis gas pre - hydrogenates the biomass to improve the subsequent reaction efficiency. The biomass pyrolysis gas discharged from the biomass pyrolysis reactor enters the co - reactor for catalytic hydrogenation reaction.

[0010] The combination of the two modes highlights the flexible regulation capability of the present application for multi-source biomass, and can select the most suitable reaction mode according to the supply amount of hydrogen-rich raw materials and the oxygen content of the biomass. It effectively solves the technical problems in the existing technology that a single reaction mode cannot adapt to the physical property differences of multi-source biomass and the hydrogen source allocation strategy is rigid and difficult to cope with the dynamic changes in raw material supply, thereby improving the system's adaptability to different biomass raw materials and the overall reaction efficiency.

[0011] Furthermore, the collaborative reactor is provided with a plurality of high-voltage electrodes arranged in a ring shape and a plurality of concentrically arranged ring-shaped grounding electrodes.

[0012] Furthermore, a conical cavity is provided at the lower portion of the co-reactor, and a spiral track is provided on the inner wall surface of the conical cavity.

[0013] The spiral track is used to ensure that the catalyst and reactants are in full contact and react, thereby improving the catalytic efficiency and helping to reduce coking.

[0014] Furthermore, the condensation system includes a plurality of condensation tanks connected in series.

[0015] Multiple condensation tanks connected in series perform multi-stage condensation on the hydrogenation product.

[0016] Furthermore, the co-reactor is connected to a reaction product exhaust pipe, the reaction product exhaust pipe is connected to a circulating gas exhaust pipe, the gas outlet end of the circulating gas exhaust pipe is connected to the co-reactor, and a circulating gas pump is installed on the circulating gas exhaust pipe.

[0017] By means of a bypass reflux cycle, part of the hydrogenation product is recycled back to the co-reactor to achieve secondary or multiple hydrogenation, thereby achieving cyclic hydrogenation and subjecting the pyrolysis gas that has not been fully reacted for the first time to a cyclic hydrogenation reaction, thereby improving the overall conversion rate.

[0018] Furthermore, it also includes a regeneration system for regenerating the spent catalyst produced by the co-reactor and re-inputting it into the co-reactor.

[0019] Furthermore, a separation system is included for separating the regenerated catalyst and hot air outputted from the regeneration system, and inputting a portion of the regenerated catalyst into the co-reactor.

[0020] The present application also provides a plasma-driven pyrolysis and upgrading method for biomass and hydrogen-rich raw materials, comprising the following steps: Hydrogen-rich feedstock and biomass pyrolysis: The hydrogen-rich feedstock and carrier gas are input into the hydrogen-rich feedstock pyrolysis reactor, and the hydrogen-rich feedstock pyrolyzes to produce hydrogen-rich feedstock pyrolysis gas and solid products; the biomass feedstock and carrier gas are input into the biomass pyrolysis reactor, and the biomass pyrolyzes to produce biomass pyrolysis gas and pyrolytic carbon; by opening or closing the valve, the gas-gas mode or gas-solid mode is selected, and the hydrogen-rich feedstock pyrolysis gas is introduced into the hydrogen-rich feedstock pyrolysis gas discharge pipeline or introduced into the biomass pyrolysis reactor through the gas inlet; Synergistic on-line upgrading and hydrogenation of pyrolysis gas: The dielectric barrier discharge technology is used to generate plasma to carry out on-line catalytic hydrodeoxygenation of pyrolysis gas; Product condensation and separation: The hydrogenation products of the plasma synergistic upgrading reaction system are separated into gas and liquid through the condensation system.

[0021] Furthermore, in the gas-gas mode, the valve is closed, and the hydrogen-rich feedstock pyrolysis gas enters the synergistic reactor through the hydrogen-rich feedstock pyrolysis gas discharge pipeline and undergoes a synergistic catalytic hydrogenation reaction with the biomass pyrolysis gas entering the synergistic reactor.

[0022] Furthermore, in the gas-solid mode, the valve is opened, and the hydrogen-rich feedstock pyrolysis gas enters the biomass pyrolysis reactor through the gas inlet and co-pyrolyzes with the biomass solid, and the hydrogen-rich feedstock pyrolysis gas pre-hydrogenates the biomass pyrolysis gas; the pyrolysis gas discharged from the biomass pyrolysis reactor enters the synergistic reactor for catalytic hydrogenation reaction.

[0023] In summary, the gas-gas / gas-solid dual-mode synergistic mechanism of the present application realizes the cascade hydrogenation of biomass pyrolysis gas and flexible distribution of hydrogen sources, and has the following remarkable advantages: 1. Wide raw material adaptability: Aiming at the oxygen-containing characteristic differences of different biomass raw materials (hardwood, herbaceous, etc.), through the flexible switching between the gas-solid mode pre-hydrogenation (applicable to high-oxygen-containing straws) and the gas-gas mode deep deoxygenation (applicable to low-oxygen-containing pinewoods), while ensuring the hydrogenation efficiency, the adaptability of the system to different biomass raw materials is improved, the raw material utilization rate is high, different from the existing single reaction mode technology, and the problem of insufficient control accuracy of oxygen-containing components is effectively solved; 2. Dynamic regulation of hydrogen source: By switching the valve to distribute the flow direction of the hydrogen-rich feedstock pyrolysis gas, the regulation method is convenient. When the hydrogen-rich feedstock is sufficient, the gas-gas mode is enabled to directly utilize its hydrogen-rich characteristics to excite the plasma and reduce the external hydrogen supply demand; when the hydrogen-rich feedstock is short, it is switched to the gas-solid mode to preferentially pre-hydrogenate the high-oxygen-containing biomass and relieve the subsequent hydrogenation pressure, ensuring the stable operation of the system under the hydrogen source fluctuation, effectively solving the problem of rigid hydrogen source distribution strategy in the existing technology, and improving the practicability and stability of the technology; 3. Improved energy efficiency and product quality: Plasma-assisted catalytic technology activates hydrogen radicals in situ through dielectric barrier discharge, achieving molecular-level reconstruction of pyrolysis gas at atmospheric pressure with high safety. Combined with the catalyst's spiral orbital structure to enhance contact, it improves hydrodeoxygenation efficiency while reducing coking. 4. Process integration and low carbonization: Through the catalyst regeneration system and heat self-supply design, the recycling of spent catalysts and the self-balance of reaction heat energy are achieved, and the overall energy consumption is lower than that of traditional multi-stage hydrogenation processes.

[0024] 5. Dual-mode synergistic combined with cyclic hydrogenation: Based on the gas-gas / gas-solid dual-mode synergistic mechanism, bypass reflux cyclic hydrogenation is carried out, and part of the hydrogenation product is recycled back to the co-reactor to achieve secondary or multiple hydrogenation, so that the cyclic hydrogenation can better adapt to different reaction stages and different raw material characteristics, further improving the overall conversion rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of the overall structure of the plasma-driven synergistic pyrolysis and upgrading system for biomass and hydrogen-rich raw materials according to an embodiment of the present application; Figure 2 This is a schematic structural diagram of a plasma-assisted upgrading reactor according to an embodiment of the present application; Figure 3 Schematic diagram of the logistics of the gas-solid mode in the plasma-driven synergistic pyrolysis and upgrading method of biomass and hydrogen-rich raw materials in an embodiment of the present application; Figure 4 It is a logistics diagram of the gas-gas mode in the plasma-driven synergistic pyrolysis and upgrading method of biomass and hydrogen-rich raw materials in an embodiment of the present application.

[0026] Reference numerals: 1, pyrolysis reaction system; 101, hydrogen-rich raw material pyrolysis reactor; 102, hydrogen-rich raw material feed port; 103, inert gas inlet I; 104, solid product outlet; 105, hydrogen-rich raw material pyrolysis gas valve; 106, biomass pyrolysis reactor; 107, biomass feed port; 108, inert gas inlet II; 109, biomass pyrolysis char outlet; 110, outlet; 111, hydrogen-rich raw material pyrolysis gas outlet; 112, gas inlet; 2. Plasma synergistic upgrading reaction system; 201. Co-reactor; 202. Catalyst inlet; 203. Regenerated catalyst inlet; 204. Spent catalyst outlet; 205. Reaction product outlet; 206. Hydrogen inlet; 207. High-voltage electrode; 208. Reaction product discharge pipe; 209. Circulating gas outlet; 210. Circulating gas inlet; 211. Circulating gas pump; 212. Condensed product discharge pipe; 213. Circulating gas discharge pipe; 214. Hydrogen-rich feedstock pyrolysis gas discharge pipe; 215. Biomass pyrolysis gas discharge pipe; 3. Condensation system; 301. First condensation tank; 302. Reaction product inlet; 303. Non-condensable gas outlet; 304. Condensed liquid outlet; 305. Second condensation tank; 306. Third condensation tank; 4. Regeneration system; 401. Catalyst regenerator; 402. Regenerated mixture outlet; 403. Spent catalyst inlet; 404. Air inlet; 405. Re-separation insulation pipeline; 406. Spent catalyst discharge pipeline; 5. Separation system; 501. Separator; 502. Air outlet; 503. Regenerated mixture inlet; 504. Catalyst regeneration outlet I; 505. Separator valve; 506. Catalyst regeneration outlet II; 507. Regenerated catalyst discharge pipeline. Detailed implementation mode

[0027] The following is a further detailed description of this application in conjunction with the attached Figures 1-4 drawings.

[0028] Example 1 The embodiment of this application discloses a plasma-driven co-pyrolysis and upgrading system for biomass and hydrogen-rich raw materials. As Figure 1 shown, the plasma-driven co-pyrolysis and upgrading system for biomass and hydrogen-rich raw materials includes a pyrolysis reaction system 1, a plasma co-upgrading reaction system 2, and a condensation system 3.

[0029] As Figure 1 shown, the pyrolysis reaction system 1 includes a hydrogen-rich raw material pyrolysis reactor 101 and a biomass pyrolysis reactor 106, which are respectively used for pyrolyzing the hydrogen-rich raw material and biomass to produce hydrogen-rich raw material pyrolysis gas and biomass pyrolysis gas. A valve 105 is connected between the hydrogen-rich raw material pyrolysis reactor 101 and the biomass pyrolysis reactor 106.

[0030] The hydrogen-rich raw material pyrolysis reactor 101 is connected with a hydrogen-rich raw material pyrolysis gas discharge pipeline 214, a gas inlet 112 is arranged on the biomass pyrolysis reactor 106, and the biomass pyrolysis reactor 106 is connected with a biomass pyrolysis gas discharge pipeline 215. When the hydrogen-rich raw material is sufficient, the valve 105 is closed, and the hydrogen-rich raw material pyrolysis gas is introduced into the hydrogen-rich raw material pyrolysis gas discharge pipeline 214 (gas-gas mode), and its hydrogen-rich characteristics are directly used to excite the plasma, reducing the external hydrogen supply demand; when the hydrogen-rich raw material is short, the valve 105 is opened, and the hydrogen-rich raw material pyrolysis gas is introduced into the biomass pyrolysis reactor 106 from the gas inlet 112 (gas-solid mode), preferentially pre-hydrogenating the high-oxygen biomass, alleviating the subsequent hydrogenation pressure, and ensuring the stable operation of the system under the hydrogen source fluctuation.

[0031] The plasma-assisted upgrading reaction system 2 includes a co-reactor 201 that generates plasma using dielectric barrier discharge technology to perform on-line catalytic hydrodeoxygenation of pyrolysis gas. The co-reactor 201 is connected to the hydrogen-rich raw material pyrolysis gas discharge pipeline 214 and the biomass pyrolysis gas discharge pipeline 215.

[0032] The condensation system 3 is used to perform gas-liquid separation on the hydrogenation products of the plasma-assisted upgrading reaction system 2.

[0033] The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis upgrading system provided in this embodiment combines gas-gas / gas-solid reactions. By exciting plasma using dielectric barrier discharge technology, a catalytic hydrogenation reaction occurs between the hydrogen-rich raw material pyrolysis gas and the biomass pyrolysis gas under atmospheric pressure conditions, achieving molecular-level co-reforming of the biomass pyrolysis gas and the hydrogen-rich raw material cracking gas to produce high-value hydrocarbon liquid fuels, improving the significant defects of the traditional process flow being long, large material losses, and high energy consumption. Moreover, the on-line upgrading reaction regulation is simple, applicable to various reaction systems with different oxygen contents in biomass and different supply amounts of hydrogen-rich raw materials, facilitating the realization of multi-reaction integration and the design of a compact reactor.

[0034] In this embodiment, as Figure 1 shown, the hydrogen-rich raw material pyrolysis reactor 101 is further provided with a hydrogen-rich raw material feed port 102, an inert gas inlet I103, a solid product outlet 104, and a hydrogen-rich raw material pyrolysis gas outlet 111.

[0035] Specifically, the hydrogen-rich raw material feed port 102 is arranged at the top of the hydrogen-rich raw material pyrolysis reactor 101 for introducing hydrogen-rich raw materials. The hydrogen-rich raw materials include but are not limited to waste plastics (such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, etc.), methanol, rubber, grease, etc., and this embodiment does not make any limitations in this regard. In the specific implementation manner of this embodiment, the hydrogen-rich raw material is waste plastic polyethylene (PE), and the pyrolysis temperature of the waste plastic is set to 500 - 800 °C. In the specific implementation manner of this embodiment, the pyrolysis temperature of the waste plastic is set to 600 °C, and the heat is self-supplied by the heat inside the hydrogen-rich raw material pyrolysis reactor 101.

[0036] Furthermore, as Figure 1 shown, the inert gas inlet I103 is arranged on the side of the pyrolysis reactor 101, and the inert gas inlet I103 is used to add inert gas, which is commonly nitrogen, argon, etc. or the tail gas that can be pyrolyzed industrially. The solid product outlet 104 is arranged at the bottom of the hydrogen-rich raw material pyrolysis reactor 101 for discharging solid products. The hydrogen-rich raw material pyrolysis gas outlet 111 is arranged at the top of the hydrogen-rich raw material pyrolysis reactor 101 and is connected to the hydrogen-rich raw material pyrolysis gas discharge pipeline 214, and the hydrogen-rich raw material pyrolysis gas outlet 111 is used to discharge hydrogen-rich raw material pyrolysis gas.

[0037] As Figure 1As shown, a biomass pyrolysis reactor 106 is further provided with a biomass feed inlet 107, an inert gas inlet II 108, an outlet 110, and a gas inlet 112.

[0038] Specifically, the biomass feed inlet 107 is arranged at the top of the biomass pyrolysis reactor 106 for the entry of biomass. The biomass includes but is not limited to crop straws, fruit peels, fruit cores, bagasse, wood chips, livestock manure, etc., and this embodiment does not make any limitation thereto. In the specific implementation manner of this embodiment, the biomass is rice straw. The biomass pyrolysis temperature is set to 400 - 800 °C. In the specific implementation manner of this embodiment, the biomass pyrolysis temperature is set to 600 °C, and the heat is self-supplied by the heat inside the biomass pyrolysis reactor 106.

[0039] Further, as Figure 1 shown, the inert gas inlet II 108 is arranged on the side of the biomass pyrolysis reactor 106. The inert gas inlet II 108 is used for adding inert gas, and commonly used ones are nitrogen, argon, etc. or the tail gas that can be pyrolyzed industrially. The biomass pyrolysis char outlet 109 is arranged at the bottom of the biomass pyrolysis reactor 106 for discharging the pyrolyzed char. The gas inlet 112 is arranged at the top of the biomass pyrolysis reactor 106 for the entry of hydrogen-rich raw material pyrolysis gas, and the gas inlet 112 is connected to the hydrogen-rich raw material pyrolysis gas outlet 111.

[0040] As Figure 1 shown, a co-reactor 201 is provided with a catalyst inlet 202, a high-voltage electrode 207, a reaction product outlet 205, and a hydrogen inlet 206.

[0041] Specifically, the top of the co-reactor 201 is connected to the outlet 110 through a biomass pyrolysis gas discharge pipe 215, and the biomass pyrolysis gas enters the co-reactor 201 through the pyrolysis gas discharge pipe 215; at the same time, the top of the co-reactor 201 is connected to a hydrogen-rich raw material pyrolysis gas discharge pipe 214, and the hydrogen-rich raw material pyrolysis gas enters the co-reactor 201 through the hydrogen-rich raw material pyrolysis gas discharge pipe 214.

[0042] Further, the catalyst inlet 202 is arranged at the top of the cylindrical cavity for adding a catalyst. The types of the catalyst include but are not limited to metal oxide catalysts, zeolite molecular sieve catalysts, etc., and different types of catalysts can be specifically selected according to the target product requirements. In this embodiment, the catalyst uses a nickel-molybdenum oxide catalyst supported by granular titanium oxide. The reaction product outlet 205 is used for discharging the hydrogenation product. The hydrogen inlet 206 is used for supplementing and introducing hydrogen.

[0043] In this embodiment, as Figure 1 and Figure 2As shown, multiple high-voltage electrodes 207 are arranged in a ring structure in the co-reactor 201, and multiple ring-shaped grounding electrodes are concentrically arranged. Both the high-voltage electrodes 207 and the grounding electrodes are coated with an insulating medium, and the materials of the insulating medium include but are not limited to quartz, ceramics, etc. High-active plasma is in-situ generated by dielectric barrier discharge in the gap between the high-voltage electrodes 207 and the grounding electrodes. The co-reactor 201 conducts on-line catalytic hydrodeoxygenation of the pyrolysis gas through the plasma and the catalyst to generate hydrogenation products.

[0044] The temperature of the on-line catalytic hydrodeoxygenation in the co-reactor 201 is 300 - 600 °C, and the heat is supplied by the heat generated by the combustion of the catalyst regenerator 401 and loaded by the regenerated catalyst.

[0045] As Figure 1 and Figure 2 shown, a conical cavity is provided at the lower part of the co-reactor 201, and the inner wall surface of the conical cavity is a spiral track. Due to different radial forces, the catalyst will spiral and roll down in the reactor cavity, enabling the catalyst to fully contact and react with the reactants, thereby improving the catalytic efficiency and helping to reduce coking, thus alleviating the problem of catalyst deactivation due to carbon deposition.

[0046] The hydrogen-rich raw material pyrolysis gas discharge pipe 214 and the biomass pyrolysis gas discharge pipe 215 are heat-insulating pipes. The waste plastic pyrolysis gas is insulated through the hydrogen-rich raw material pyrolysis gas discharge pipe 214, and the biomass pyrolysis gas is insulated through the biomass pyrolysis gas discharge pipe 215.

[0047] In this embodiment, as Figure 1 and Figure 2 shown, a waste catalyst outlet 204 is provided at the bottom of the co-reactor 201. Specifically, the waste catalyst outlet 204 is provided at the bottom of the conical cavity for discharging the waste catalyst.

[0048] As Figure 1 shown, a reaction product discharge pipe 208 is also connected to the bottom of the co-reactor 201. A reaction product outlet 205 is provided on the side of the reaction product discharge pipe 208, and a waste catalyst outlet 204 is provided at the bottom end of the reaction product discharge pipe 208. The reaction product discharge pipe 208 is arranged vertically so that solid particles (waste catalyst) sink and are discharged along the reaction product discharge pipe 208, and the reaction product (gaseous) is extracted from the side of the reaction product discharge pipe 208.

[0049] The condensation system 3 includes a first condensation tank 301, a second condensation tank 305, and a third condensation tank 306 connected in series. A reaction product inlet 302 is provided on the first condensation tank 301, and a condensed liquid outlet 304 and a non-condensable gas outlet 303 are provided on the third condensation tank 306. The reaction product inlet 302 is communicated with the reaction product outlet 205. The reaction product enters the first condensation tank 301 through the reaction product inlet 302. The first condensation tank 301, the second condensation tank 305, and the third condensation tank 306 are successively used to condense the reaction product to obtain condensed liquid and non-condensable gas. The condensed liquid outlet 304 is used to discharge the condensed liquid, and the non-condensable gas outlet 303 is used to discharge the non-condensable gas.

[0050] In this embodiment, both the condensed liquid and the non-condensable gas are effective products. Among them, the pyrolytic carbon can be used to prepare carbon materials including but not limited to carbon fertilizers, activated carbon, carbon electrodes, etc. The condensed liquid includes but not limited to one or more of aromatic hydrocarbons, alkanes, and alkenes according to different catalysts used. The non-condensable gas mainly consists of CO2, CO, and a small amount of lower hydrocarbons, and can be used as gas fuel or chemical raw materials, etc. subsequently.

[0051] In this embodiment, as Figure 1 shown, it further includes a condensed product discharge pipeline 212 and a recycle gas discharge pipeline 213. The hydrogenated product is divided into a first part and a second part. One end of the condensed product discharge pipeline 212 is connected to the reaction product outlet 205, and the other end of the condensed product discharge pipeline 212 is connected to the reaction product inlet 302, so that the first part of the reaction product is discharged into the first condensation tank 301. A recycle gas outlet 209 is provided on the condensed product discharge pipeline 212, and a recycle gas inlet 210 is provided on the co-reactor 201. One end of the recycle gas discharge pipeline 213 is connected to the recycle gas outlet 209, and the other end of the recycle gas discharge pipeline 213 is connected to the recycle gas inlet 210, so that the second part of the hydrogenated product enters the co-reactor 201 for recycle hydrogenation.

[0052] In this embodiment, both the condensed product discharge pipeline 212 and the recycle gas discharge pipeline 213 are heat-insulating pipelines, which are respectively used to keep the first part of the hydrogenated product and the second part of the hydrogenated product warm.

[0053] Through the way of bypass reflux circulation, part of the hydrogenated product is recycled back to the co-reactor 201 to achieve secondary or multiple hydrogenations, and the pyrolysis gas that was not completely reacted for the first time is subjected to recycle hydrogenation reaction, thereby improving the overall conversion rate.

[0054] Further, as Figure 1As shown, a recycle gas pump 211 is provided on the recycle gas discharge pipeline 213. The recycle gas pump 211 is used to extract the second part of the hydrogenated product for recycle hydrogenation. The ratio of hydrogenated product condensation to recycle is controlled by the power of the recycle gas pump 211, and the recycle flow rate through the recycle pump does not exceed 80% of the flow rate of the reaction product flowing out of the reaction product outlet 205.

[0055] As Figure 1 shown, the plasma-driven biomass and hydrogen-rich raw material co-pyrolysis upgrading system provided by the embodiment of the present application further includes a regeneration system 4, which is used to regenerate the waste catalyst generated by the co-reactor 201 and re-enter it into the co-reactor 201.

[0056] Specifically, as Figure 1 shown, the regeneration system 4 includes a waste catalyst discharge pipeline 406 and a catalyst regenerator 401. The catalyst regenerator 401 is provided with a regeneration mixture outlet 402, a waste catalyst inlet 403, and an air inlet 404. One end of the waste catalyst discharge pipeline 406 is connected to the bottom end of the reaction product discharge pipeline 208, and the other end of the waste catalyst discharge pipeline 406 is connected to the feed end of the catalyst regenerator 401 so that the waste catalyst enters the catalyst regenerator 401. The waste catalyst discharge pipeline 406 is inclined at a certain angle to facilitate the waste catalyst to slide into the catalyst regenerator 401. The catalyst regenerator 401 is used to remove the carbon deposits on the waste catalyst to generate a regenerated catalyst, and the discharge end of the catalyst regenerator 401 is connected to the co-reactor 201 so that the regenerated catalyst re-enters the co-reactor 201. The regeneration mixture outlet 402 is used to discharge the regenerated catalyst mixed with hot air, and the air inlet 404 is used to introduce air.

[0057] Among them, the waste catalyst discharge pipeline 406 is a heat-insulating pipeline to ensure heat insulation of the waste catalyst by the waste catalyst discharge pipeline 406.

[0058] As Figure 1 shown, a separation system 5 is connected to the discharge end of the regeneration system 4. The separation system 5 is arranged between the catalyst regenerator 401 and the co-reactor 201. The separation system 5 is used to separate the regenerated catalyst and hot air, and input a part of the regenerated catalyst into the co-reactor 201.

[0059] Specifically, as Figure 1As shown, the separation system 5 includes a separator 501, an air outlet 502, a regeneration mixture inlet 503, a catalyst regeneration outlet I 504, and a catalyst regeneration outlet II 506. The separator 501 is used to separate the hot air mixed in the regenerated catalyst to air-dry the regenerated catalyst. The separator 501 generates a first part of the regenerated catalyst and a second part of the regenerated catalyst. The regeneration mixture inlet 503 is connected to the regeneration mixture outlet 402 through a re-insulated pipeline 405 so that the regenerated catalyst enters the separator 501. The air outlet 502 is used to discharge the hot air. The catalyst regeneration outlet I 504 is connected to the regenerated catalyst inlet 203 on the co-reactor 201 through a regenerated catalyst discharge pipeline 507 so that the first part of the regenerated catalyst enters the co-reactor 201. The catalyst regeneration outlet II 506 is used to discharge the second part of the regenerated catalyst.

[0060] In this embodiment, the regenerated catalyst discharge pipeline 507 is an insulated pipeline to ensure heat preservation of the first part of the regenerated catalyst by the regenerated catalyst discharge pipeline 507.

[0061] As Figure 1 shown, the separation system 5 further includes a separator valve 505. The bottom of the separator 501 is provided with a discharge port. The separator valve 505 is provided with one inlet and two outlets. The inlet of the separator valve 505 is connected to the discharge port of the separator 501. One of the outlets of the separator valve 505 serves as the catalyst regeneration outlet I 504 to discharge the first part of the regenerated catalyst and is connected to the regenerated catalyst inlet 203. The other outlet of the separator valve 505 serves as the catalyst regeneration outlet II 506 to discharge the second part of the regenerated catalyst. The discharge time and flow rate of the first part of the regenerated catalyst and the second part of the regenerated catalyst can be determined by the engineering effect.

[0062] In this embodiment, the catalyst regenerator 401 is a riser structure. By introducing air for combustion reaction and carrying particles upward into the separation system 5, the carbon deposition on the spent catalyst is eliminated by combustion. Most of the heat generated by the combustion is carried by the hot catalyst particles into the co-reactor 201 to maintain the hydrogenation reaction temperature.

[0063] In summary, the present application combines gas-gas / gas-solid synergy reaction modes, and the two modes can be flexibly switched, enabling dynamic regulation of the hydrogen source. While ensuring the biomass hydrogenation efficiency, it improves the adaptability of the system to different biomass raw materials, with high raw material utilization rate. By exciting plasma through dielectric barrier discharge, a catalytic hydrogenation reaction occurs between the pyrolysis gas of hydrogen-rich raw materials and the biomass pyrolysis gas under atmospheric pressure conditions, realizing molecular-level synergistic reforming of the biomass pyrolysis gas and the pyrolysis gas of hydrogen-rich raw materials to produce high-value hydrocarbon liquid fuels, improving the significant defects of the traditional process such as long process flow, large material loss, and high energy consumption. Moreover, the on-line upgrading reaction regulation is simple, which is conducive to the realization of multi-reaction integration and the design of a compact reactor.

[0064] Through the reactor structure design, the utilization efficiency of the catalyst can be achieved in the present application. The lower part of the synergy reactor 201 adopts a conical shape with an inclined angle, and the inner wall surface of the conical cavity is a spiral track. Due to different radial forces, the catalyst can roll and sink in the reactor, enabling the catalyst to fully contact and react with the reactants, thereby improving the catalytic efficiency and alleviating the problem of catalyst carbon deposition deactivation. The catalyst regenerator 401 adopts a riser structure, which can eliminate the carbon deposition on the waste catalyst through combustion and introduce it into the separator 501. The separated catalyst particles can be continuously put into the synergy reactor 201 for use.

[0065] By means of bypass reflux circulation, the present application can recycle part of the hydrogenation products back to the synergy reactor 201 for secondary or multiple hydrogenations, and can carry out cyclic hydrogenation reactions on the pyrolysis gas that was not fully reacted for the first time, thereby improving the overall conversion rate. In addition, by means of riser combustion, catalyst recycling and regeneration can be realized, the catalyst can be recycled, the amount of catalyst added at the catalyst inlet can be reduced, and the overall process economy can be improved.

[0066] In the present application, heat is self-supplied to the synergy reactor 201 through the heat self-supply of the hydrogen-rich raw material pyrolysis reactor 101 and the biomass pyrolysis reactor 102, as well as the heat supply during the catalyst regeneration process, without external heat supply, realizing the heat self-supply of the entire process. The high-voltage electrode 207 used in the present application can not only be powered by the power grid, but also be driven by renewable energy electricity such as wind power, photovoltaic power, and hydropower, realizing the immediate local consumption of renewable energy electricity, solving the instability of renewable energy electricity, and further realizing the clean and low-carbon of the overall process.

[0067] Example 2 The embodiment of the present application discloses a method for synergistic pyrolysis and upgrading of biomass and hydrogen-rich raw materials driven by plasma, using the plasma-driven synergistic pyrolysis and upgrading system of biomass and hydrogen-rich raw materials disclosed in Example 1, as Figure 3 and Figure 4 shown. The method includes the following steps: S1: Hydrogen-rich feedstock and biomass pyrolysis: Input the hydrogen-rich feedstock and the drying carrier gas into the hydrogen-rich feedstock pyrolysis reactor 101. Achieve the pyrolysis of the hydrogen-rich feedstock and heat self-supply by ignition and controlling the air volume, so that the hydrogen-rich feedstock pyrolyzes to produce hydrogen-rich feedstock pyrolysis gas and solid products. Input the dried biomass feedstock and the drying carrier gas into the biomass pyrolysis reactor 106. Achieve the pyrolysis of the biomass and heat self-supply by ignition and controlling the air volume, so that the biomass pyrolyzes to produce biomass pyrolysis gas and pyrolytic carbon.

[0068] S2-1: Gas-solid mode: When the hydrogen-rich feedstock is in short supply, open the hydrogen-rich feedstock pyrolysis gas valve 105. The hydrogen-rich feedstock pyrolysis gas is discharged from the hydrogen-rich feedstock pyrolysis gas outlet 111, enters the biomass pyrolysis reactor 106 through the gas inlet 112, and undergoes a co-pyrolysis reaction with the biomass solid. The hydrogen-rich feedstock pyrolysis gas pre-hydrogenates the biomass pyrolysis gas. S2-2: Gas-gas mode: When the hydrogen-rich feedstock is sufficient, close the hydrogen-rich feedstock pyrolysis gas valve 105. The hydrogen-rich feedstock pyrolysis gas will be discharged from the hydrogen-rich feedstock pyrolysis gas outlet 111 and enter the co-reactor 201 through the hydrogen-rich feedstock pyrolysis gas discharge pipeline 214. The biomass pyrolysis gas generated by the biomass pyrolysis reactor 106 enters the co-reactor 201 through the biomass pyrolysis gas discharge pipeline 215.

[0069] S2: Co-pyrolysis gas synergistic in-situ upgrading and hydrogenation: The catalyst enters the co-reactor 201 from the catalyst inlet 202. High-energy plasma is in-situ generated by dielectric barrier discharge between the high-voltage electrode 207 and the grounded electrode. In the co-reactor 201, the pyrolysis gas is catalytically hydrogenated and deoxygenated in-situ to generate hydrogenated products and waste catalysts. The reaction product outlet 208 is used to discharge the reaction products.

[0070] S3: Product condensation and separation: The reaction products of the co-reactor 201 are discharged from the reaction product outlet 208 and then enter the first condenser 301, the second condenser 305, and the third condenser 306 in sequence through the reaction product inlet 302 for condensation. The condensed liquid is discharged through the condensed liquid outlet 304, and the non-condensable gas is discharged through the non-condensable gas outlet 303.

[0071] In this embodiment, when cyclic hydrogenation is required, it further includes step S4: Product cyclic hydrogenation: The first part of the hydrogenated products discharged from the reaction product outlet 205 enters the first condenser 301 through the condensed product discharge pipeline 212 from the reaction product inlet 302. The second part of the hydrogenated products is pumped back to the recycle gas inlet 210 by the recycle gas pump 211 provided on the recycle gas discharge pipeline 213 and re-enters the co-reactor 201 to perform step S2.

[0072] In this embodiment, when a regeneration system 4 is provided, it further includes step S5: catalyst circulation and regeneration. The waste catalyst enters the catalyst regenerator 401 from the waste catalyst inlet 403 after passing through the reaction product discharge pipe 208 and the waste catalyst discharge pipe 406. Air enters the catalyst regenerator 401 from the air inlet 404. The waste catalyst particles and air undergo a combustion reaction, and the carbon deposits on the waste catalyst are removed. The regeneration mixture enters the separator 501 from the regeneration mixture outlet 402 to achieve gas-solid separation. The hot air is discharged from the air outlet 502 at the upper end, and the regenerated catalyst is discharged from the regenerated catalyst outlet I504. After passing through the regenerated catalyst discharge pipe 507, it enters the co-reactor 201 through the regenerated catalyst inlet 203 to perform step S2.

[0073] In summary, for the plasma-driven collaborative pyrolysis and upgrading method of biomass and hydrogen-rich raw materials disclosed in this embodiment, by switching the flow direction of the hydrogen-rich raw material pyrolysis gas through valves, flexible switching between the gas-gas / gas-solid modes and dynamic regulation of the hydrogen source are achieved. While ensuring the hydrogenation efficiency, the adaptability of the system to different biomass raw materials is improved, and the raw material utilization rate is high.

[0074] The above are all preferred embodiments of this application. The protection scope of this application is not limited by this. Therefore, all equivalent changes made according to the structure, shape, and principle of this application should be covered within the protection scope of this application.

Claims

1. A plasma-driven co-pyrolysis upgrading system for biomass and hydrogen-rich raw materials, characterized in that: Comprising: A pyrolysis reaction system, including a hydrogen-rich raw material pyrolysis reactor, a biomass pyrolysis reactor, and a valve connected between the two. The hydrogen-rich raw material pyrolysis reactor is connected to a hydrogen-rich raw material pyrolysis gas discharge pipeline. A gas inlet is provided on the biomass pyrolysis reactor. The biomass pyrolysis reactor is connected to a biomass pyrolysis gas discharge pipeline. The valve is used to introduce the hydrogen-rich raw material pyrolysis gas discharged from the hydrogen-rich raw material pyrolysis reactor into the hydrogen-rich raw material pyrolysis gas discharge pipeline or into the biomass pyrolysis reactor through the gas inlet; A plasma-assisted upgrading reaction system, including a co-reactor that generates plasma using dielectric barrier discharge technology to perform on-line catalytic hydrodeoxygenation on the pyrolysis gas. The co-reactor is connected to the hydrogen-rich raw material pyrolysis gas discharge pipeline and the biomass pyrolysis gas discharge pipeline; A condensation system for performing gas-liquid separation on the hydrogenation products of the plasma-assisted upgrading reaction system.

2. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis and upgrading system according to claim 1, wherein: A plurality of annularly arranged high-voltage electrodes and a plurality of concentrically arranged annular ground electrodes are provided inside the co-reactor.

3. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis and upgrading system according to claim 1, wherein: A conical cavity is provided at the lower part of the co-reactor, and a spiral track is provided on the inner wall surface of the conical cavity.

4. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis and upgrading system according to claim 1, wherein: The condensation system includes a plurality of serially connected condensation tanks.

5. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis and upgrading system according to claim 1, wherein: The co-reactor is connected to a reaction product discharge pipeline, the reaction product discharge pipeline is connected to a recycle gas discharge pipeline, the outlet end of the recycle gas discharge pipeline is connected to the co-reactor, and a recycle gas pump is installed on the recycle gas discharge pipeline.

6. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis and upgrading system according to claim 1, wherein: It further includes a regeneration system for regenerating the waste catalyst generated by the co-reactor and re-introducing it into the co-reactor.

7. The plasma-driven biomass and hydrogen-rich raw material co-pyrolysis upgrading system according to claim 6, wherein: It further includes a separation system for separating the regenerated catalyst and hot air output by the regeneration system and inputting a part of the regenerated catalyst into the co-reactor.

8. A method for co-pyrolysis upgrading of biomass and hydrogen-rich raw materials driven by plasma, which uses the plasma-driven co-pyrolysis upgrading system of biomass and hydrogen-rich raw materials described in any one of claims 1-7, and is characterized in that: Including the following steps: Hydrogen-rich raw material and biomass pyrolysis: Input the hydrogen-rich raw material and carrier gas into the hydrogen-rich raw material pyrolysis reactor, and the hydrogen-rich raw material pyrolyzes to produce hydrogen-rich raw material pyrolysis gas and solid products; Input the biomass raw material and carrier gas into the biomass pyrolysis reactor, and the biomass pyrolyzes to produce biomass pyrolysis gas and pyrolysis carbon; By opening or closing the valve, select the gas-gas mode or gas-solid mode, and introduce the hydrogen-rich raw material pyrolysis gas into the hydrogen-rich raw material pyrolysis gas discharge pipeline or into the biomass pyrolysis reactor through the gas inlet; Synergistic on-line upgrading and hydrogenation of pyrolysis gas: Generate plasma using dielectric barrier discharge technology to perform on-line catalytic hydrodeoxygenation on the pyrolysis gas; Product condensation and separation: Perform gas-liquid separation on the hydrogenation products of the plasma-assisted upgrading reaction system through the condensation system.

9. The plasma-driven co-pyrolysis upgrading method of biomass and hydrogen-rich raw materials according to claim 8, wherein: In the gas-gas mode, the valve is closed, and the hydrogen-rich raw material pyrolysis gas enters the co-reactor through the hydrogen-rich raw material pyrolysis gas discharge pipeline and undergoes a synergistic catalytic hydrogenation reaction with the biomass pyrolysis gas entering the co-reactor.

10. The plasma-driven co-pyrolysis and upgrading method of biomass and hydrogen-rich raw materials according to claim 8, characterized in that: In the gas-solid mode, the valve is opened, and the hydrogen-rich raw material pyrolysis gas enters the biomass pyrolysis reactor through the gas inlet and undergoes a co-pyrolysis reaction with the biomass solid, and the hydrogen-rich raw material pyrolysis gas pre-hydrogenates the biomass pyrolysis gas; The pyrolysis gas discharged from the biomass pyrolysis reactor enters the co-reactor for catalytic hydrogenation reaction.

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