Coaxial double-zone plasma coupling type pyrolysis online hydrogenation reaction device and method

Abstract

The invention provides a coaxial double-zone plasma coupling type pyrolysis online hydrogenation reaction device and method. The coaxial double-zone plasma coupling type pyrolysis online hydrogenation reaction device mainly comprises a plasma auxiliary pyrolysis reaction unit and a plasma online hydrogenation reaction unit. The plasma-assisted pyrolysis reaction unit is used for realizing efficient pyrolysis of biomass, a pyrolysis high-voltage electrode and a pyrolysis grounding electrode are arranged in a cavity of the plasma-assisted pyrolysis reaction unit, plasma is generated through dielectric barrier discharge, and pyrolysis is assisted to obtain pyrolysis gas with small molecular weight. The plasma on-line hydrogenation reaction unit is used for realizing on-line hydrogenation quality improvement of pyrolysis gas, a hydrogenation high-voltage electrode and a hydrogenation grounding electrode are arranged in a cavity of the plasma on-line hydrogenation reaction unit, hydrogen is excited through dielectric barrier discharge to generate hydrogen plasma, and the pretreated pyrolysis gas is subjected to catalytic hydrogenation. Compared with the traditional process, the integrated and compact design of pyrolysis and hydrogenation reaction units is realized, the space is saved, the energy consumption and material loss are effectively reduced through online hydrogenation, and a feasible technical path is provided for efficient utilization of biomass.

Description

Technical Field

[0001] The present invention relates to the technical field of biomass resource utilization, and particularly to a coaxial dual-zone plasma-coupled pyrolysis in-situ hydrogenation reactor device and method. Background Art

[0002] As the only carbon-containing renewable resource at present, biomass has received extensive attention in the fields of green energy and waste resource utilization. Biomass pyrolysis, as a mature industrial biomass treatment technology, can convert biomass into three-phase products of oil, gas, and char in a short time, with advantages such as strong raw material adaptability, fast reaction rate, less secondary pollution, and energy self-supply, making it a relatively popular treatment method at present. Moreover, the gaseous volatile components generated during pyrolysis contain a large amount of oxygenated unsaturated components, which can be further converted into high-quality liquid fuels such as aromatics and alkanes through reactions such as hydrodeoxygenation and condensation.

[0003] Currently, traditional biomass pyrolysis-hydrogenation processes generally adopt a segmented reaction system, and the pyrolysis and hydrogenation processes need to be completed in separate equipment in segments. Specifically, the volatile components generated by the pyrolysis reactor need to be first converted into liquid bio-oil through a condensation system, and then transported through pipelines to a separately arranged autoclave hydrogenation reactor for reheating and catalytic hydrogenation. In this process, the two reactors need to be repeatedly configured with heating modules, pressure control systems, and catalyst loading units, resulting in a large floor area of the equipment and redundant functional modules; at the same time, substances are prone to condensation during the process of reheating after the volatile components are condensed into bio-oil, and significant heat energy loss will occur, directly affecting the yield. In addition, the hydrogenation reaction kettle needs to rely on high-pressure conditions to maintain the hydrogenation efficiency, not only requiring a complex high-pressure hydrogen supply system and multi-stage compressors, but also further increasing the equipment cost and operation risk due to the requirements of high-pressure sealing and safety protection.

[0004] Therefore, how to break through the technical bottlenecks of low space utilization rate and high consumption of materials caused by the independent operation of pyrolysis and hydrogenation equipment in traditional segmented multi-step processes, realize the integrated and collaborative treatment of pyrolysis and hydrogenation through reactor structure innovation, improve the space utilization efficiency of the reactor while reducing equipment redundancy, and reduce system energy consumption and material loss has become an important technical issue in the development of biomass high-efficiency conversion technology. Summary of the Invention

[0005] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a coaxial dual-zone plasma-coupled pyrolysis in-situ hydrogenation reactor device and method, mainly by integrating the pyrolysis and hydrogenation units into one reactor, and carrying out catalytic hydrogenation reactions between active hydrogen plasma and gaseous pyrolysis products under atmospheric pressure, with lower overall losses and energy consumption, and more secure atmospheric pressure operation.

[0006] To solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0007] A coaxial dual-zone plasma-coupled pyrolysis on-line hydrogenation device, comprising:

[0008] A plasma-assisted pyrolysis reaction unit, including a pyrolysis reactor. Inside the cavity of the pyrolysis reactor, a pyrolysis high-voltage electrode and a pyrolysis grounding electrode are arranged, which are used to perform pyrolysis reaction on biomass to generate pyrolytic carbon, waste pyrolysis catalyst and pretreated pyrolysis gas. The pretreated pyrolysis gas is discharged through the pyrolysis gas vent hole;

[0009] A plasma on-line hydrogenation reaction unit, including a hydrogenation reactor arranged coaxially with the pyrolysis reactor. Inside the cavity of the hydrogenation reactor, a hydrogenation high-voltage electrode and a hydrogenation grounding electrode are arranged, which are used to perform on-line catalytic hydrogenation reaction on the pretreated pyrolysis gas to generate hydrogenation products and waste hydrogenation catalyst. The hydrogenation products and the waste hydrogenation catalyst are separated and discharged through the second discharge port.

[0010] Further, the pyrolysis reactor is communicated with the hydrogenation reactor through the pyrolysis gas vent hole. The pretreated pyrolysis gas is directly discharged through the pyrolysis gas vent hole and enters the plasma on-line hydrogenation reaction unit on-line.

[0011] Further, the pyrolysis high-voltage electrode is connected to a variable-frequency high voltage, and high-voltage discharge is carried out through the pyrolysis grounding electrode and the insulating media coated on their surfaces. Uniform plasma is generated by dielectric barrier discharge technology to realize the preliminary upgrading of pyrolysis gas to obtain pyrolysis gas with a smaller molecular weight; the hydrogenation high-voltage electrode is connected to a variable-frequency high voltage, and high-voltage discharge is carried out through the hydrogenation grounding electrode and the insulating media coated on their surfaces. Uniform hydrogen plasma is generated by dielectric barrier discharge technology to realize the on-line hydrogenation upgrading of the pretreated pyrolysis gas.

[0012] Further, the plasma-assisted pyrolysis reaction unit is also provided with a first feed port and a first discharge port; wherein, the first feed port is used to add biomass raw materials and pyrolysis catalyst, and after pyrolysis reaction, pyrolytic carbon, waste pyrolysis catalyst and pretreated pyrolysis gas are generated; the pyrolytic carbon and the waste pyrolysis catalyst are discharged through the first discharge port.

[0013] Further, the lower part of the hydrogenation reactor is designed as a conical cavity structure.

[0014] Further, the hydrogenation reactor is also provided with a second feed port for adding hydrogenation catalyst; at the same time, a third feed port is provided for introducing hydrogen required for the reaction; the second feed port is in a circular ring shape, and the top structure of the pyrolysis reactor is in a frustum shape.

[0015] Further, the high-pressure hydrogenation electrode is arranged between the pyrolysis reactor and the hydrogenation reactor cavity, and is distributed in a coaxial and equally angled manner, and can be arranged in one or more circles.

[0016] Further, it also includes a second discharge port, the top of which is communicated with the bottom of the conical cavity structure of the hydrogenation reactor. A hydrogenation product outlet is arranged on the side of the second discharge port, and a spent catalyst outlet is arranged at the bottom of the second discharge port.

[0017] Further, the hydrogenation product outlet is connected to a fan, and the hydrogenation product is stably extracted through a negative pressure system.

[0018] On the other hand, the present invention provides a coaxial dual-zone plasma integrated coupling type pyrolysis on-line hydrogenation reaction method, which includes the following steps:

[0019] (1) Plasma-assisted biomass pyrolysis

[0020] The biomass raw material and the pyrolysis catalyst are added into the pyrolysis reactor through the first feed port. Under the action of the pyrolysis high-pressure electrode and the pyrolysis grounding electrode, the biomass undergoes a pyrolysis reaction to generate pyrolytic carbon, spent pyrolysis catalyst and pre-treated pyrolysis gas with reduced molecular weight; the pyrolytic carbon and the spent pyrolysis catalyst are discharged from the first discharge port, while the pyrolysis gas is discharged through the pyrolysis gas vent hole and directly enters the plasma on-line hydrogenation reaction unit;

[0021] (2) Hydrogen introduction and hydrogen plasma excitation

[0022] In the hydrogenation reactor, hydrogen is introduced through the third feed port, and at the same time, the hydrogen is excited by the electric field formed between the high-pressure hydrogenation electrode and the hydrogenation grounding electrode to generate hydrogen plasma;

[0023] (3) Atmospheric pressure on-line catalytic hydrogenation reaction

[0024] The hydrogenation catalyst is evenly added through the second feed port arranged on the hydrogenation reactor, so that the hydrogenation catalyst is fully mixed with the hydrogen plasma and the incoming pre-treated pyrolysis gas, and an on-line catalytic hydrogenation reaction is realized under atmospheric pressure conditions to generate hydrogenation products and spent hydrogenation catalysts;

[0025] (4) Product discharge and separation

[0026] The hydrogenation products and the spent hydrogenation catalysts after the reaction are discharged through the spent catalyst outlet and the hydrogenation product outlet of the hydrogenation reactor respectively after passing through the second discharge port; the hydrogenation product outlet is connected to a fan, and the hydrogenation products are continuously and stably extracted through a negative pressure system, and the hydrogenation products are further sent to a subsequent device for condensation separation to obtain liquid and gas products.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] Compared with the traditional process, the present invention realizes the integrated and compact design of the pyrolysis and hydrogenation reaction units, overcomes the defects of large floor area and high consumption of consumables caused by the decentralized layout of traditional equipment, saves space, and effectively reduces energy consumption and material loss through on-line hydrogenation, providing a feasible technical path for the efficient utilization of biomass. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings described herein are used to provide a further understanding of the present invention and form a part of this application. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0030] Figure 1 is a schematic diagram of the coaxial dual-zone integrated coupling pyrolysis on-line hydrogenation reactor device of the present invention;

[0031] Figure 2 is a top view of the coaxial dual-zone integrated coupling pyrolysis on-line hydrogenation reactor device of the present invention;

[0032] Figure 3 is a process flow diagram of the coaxial dual-zone integrated coupling pyrolysis on-line hydrogenation reactor of the present invention.

[0033] Among them, 1 is the plasma-assisted pyrolysis reaction unit; 11 is the pyrolysis reactor; 111 is the internal pyrolysis high-voltage electrode; 112 is the pyrolysis grounding electrode coated on the inner wall; 113 is the first feed port; 114 is the first discharge port; 115 is the pyrolysis gas vent hole;

[0034] 2 is the plasma on-line hydrogenation reaction unit; 21 is the hydrogenation reactor; 211 is the hydrogenation high-voltage electrode; 212 is the hydrogenation grounding electrode; 213 is the second feed port; 214 is the third feed port; 215 is the conical cavity structure; 216 is the second discharge port;

[0035] 301 is the fan; DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.

[0037] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first", "second", etc. may explicitly or implicitly include one or more of such features. In the description of the present invention, unless otherwise specified, the meaning of "a plurality" is two or more.

[0038] Example 1

[0039] In the related art, the traditional biomass pyrolysis-hydrogenation process generally uses a segmented reaction system, and the pyrolysis and hydrogenation processes need to be completed in separate equipment in segments. Specifically, the volatile matter generated by the pyrolysis reactor needs to be first converted into liquid bio-oil through a condensation system, and then transported through a pipeline to a separately arranged autoclave hydrogenation reactor for reheating and catalytic hydrogenation. In this process, the two sets of reactors need to repeatedly configure heating modules, pressure control systems, and catalyst loading units, resulting in a large floor area of the equipment and redundant functional modules; at the same time, substances are prone to polycondensation during the process of reheating after the volatile matter is condensed into bio-oil, and significant heat energy loss will occur, directly affecting the yield. In addition, the hydrogenation reactor needs to rely on high-pressure conditions to maintain the hydrogenation efficiency. It not only needs to be equipped with a complex high-pressure hydrogen supply system and a multi-stage compressor, but also further increases the equipment cost and operation risk due to the requirements of high-pressure sealing and safety protection.

[0040] In view of the above problems, how to break through the technical bottlenecks of low space utilization rate and high consumption of consumables caused by the independent operation of pyrolysis and hydrogenation equipment in the traditional segmented process, realize on-line hydrogenation of pyrolysis volatiles and directional regulation of products through reactor structure innovation, avoid the condensation-reheating process, replace the segmented reactor with a compact integrated design, eliminate equipment redundancy and improve space utilization efficiency, and at the same time reduce system energy consumption and operating pressure, has become the core challenge in the development of biomass high-efficiency conversion technology.

[0041] Example 1 provides a coaxial dual-zone plasma-coupled pyrolysis on-line hydrogenation reaction device; this device includes a plasma-assisted pyrolysis reaction unit 1 and a plasma on-line hydrogenation reaction unit 2.

[0042] The plasma-assisted pyrolysis reaction unit 1 includes a pyrolysis reactor 11. The biomass raw material and the pyrolysis catalyst enter the pyrolysis reactor 11 through the first feed port (pyrolysis raw material and pyrolysis catalyst inlet) 113, and the pyrolysis reaction occurs therein. Inside the cavity of the pyrolysis reactor, a pyrolysis high-voltage electrode 111 and a pyrolysis grounding electrode 112 are arranged. These electrodes use dielectric barrier discharge technology to excite and generate plasma-assisted pyrolysis, reduce the molecular weight of the pyrolysis gas, and generate pyrolytic carbon and pretreated pyrolysis gas; the pyrolytic carbon and the waste pyrolysis catalyst are discharged through the first discharge port (pyrolytic carbon and waste pyrolysis catalyst outlet) 114, and the pyrolysis gas enters the on-line hydrogenation unit 2 through the pyrolysis gas vent hole 115.

[0043] The plasma on-line hydrogenation reaction unit 2 includes a hydrogenation reactor 21; the hydrogenation reactor 21 is coaxially arranged with the pyrolysis reactor 11, and a cylindrical hydrogenation high-voltage electrode 211 is provided between the two. Hydrogenation grounding electrodes 212 are respectively arranged on the outer side and the inner side of the hydrogenation reactor; the hydrogenation catalyst is evenly added into the hydrogenation reactor 21 through the second feed port (hydrogenation catalyst inlet) 213, and hydrogen is introduced through the third feed port 214; inside the hydrogenation reactor 21, hydrogen is excited into hydrogen plasma under the action of an electric field, and fully contacts with the pretreated pyrolysis gas and the hydrogenation catalyst to carry out on-line catalytic hydrogenation reaction to generate hydrogenation products; the lower part of the hydrogenation reactor 21 is designed as a conical cavity structure 215 to facilitate the discharge and separation of the hydrogenation products and the waste hydrogenation catalyst. The hydrogenation products and the waste hydrogenation catalyst are separated through the second discharge port 216, and the hydrogenation product outlet is connected to a blower, and the hydrogenation products are stably extracted through a negative pressure system.

[0044] Through this device, biomass is pyrolyzed in the plasma-assisted pyrolysis reaction unit 1 to generate pretreated pyrolysis gas. Subsequently, in the plasma on-line hydrogenation reaction unit 2, the pretreated pyrolysis gas reacts with hydrogen plasma and the hydrogenation catalyst to carry out on-line catalytic hydrogenation reaction to generate hydrogenation products. This design realizes gas-phase on-line normal-pressure hydrogenation, uses hydrogen plasma as the reaction hydrogen source, and carries out catalytic hydrogenation reaction with the gas-phase pyrolysis products. The overall loss and energy consumption are lower, and the normal-pressure operation is safer.

[0045] This embodiment provides a coaxial double-zone plasma-coupled pyrolysis on-line hydrogenation reactor device and its method. By using the hydrogen plasma generated by the electric field between the hydrogenation high-voltage electrode and the hydrogenation grounding electrode as the reaction hydrogen source, on-line catalytic hydrodeoxygenation reaction of biomass pyrolysis gas is realized in the gas phase. This system organically integrates biomass pyrolysis and hydrogenation reactions, effectively avoiding the problems of long process flow, large material loss, and high energy consumption caused by first condensing pyrolysis gas into bio-oil and then using a high-pressure hydrogenation system for deoxygenation in the traditional process. At the same time, the normal-pressure on-line reaction makes the process control more convenient, helps to integrate multiple reactions, and is convenient for designing a compact and efficient reactor.

[0046] In this embodiment, as Figure 1 shown, a first feed port 113 and a first discharge port 114 are further provided on the pyrolysis reactor 11 in the plasma-assisted pyrolysis reaction unit 1. The first feed port 113 is arranged at the top of the pyrolysis reactor 11 and is used to introduce biomass raw materials and pyrolysis catalysts. The biomass raw materials include but are not limited to corn straw, rice straw, wood chips, rice husks, etc.; in this embodiment, corn straw is specifically used as an example. Inside the pyrolysis reactor 11, there are a pyrolysis high-voltage electrode 111 and a pyrolysis grounding electrode 112 coated on the inner wall; the pyrolysis high-voltage electrode is connected to a variable-frequency high voltage, and high-voltage discharge is carried out through the pyrolysis grounding electrode and the insulating medium coated on their surfaces, and uniform plasma is generated by dielectric barrier discharge technology to achieve preliminary upgrading of pyrolysis gas to obtain pyrolysis gas with a smaller molecular weight. The reaction temperature in the pyrolysis reactor is strictly limited between 400 - 500 °C, and is specifically set to 450 °C in this embodiment. The heat required for the reaction is supplied by the heating resistor provided in the pyrolysis reactor 11; the first discharge port (pyrolysis carbon outlet) 114 is arranged at the bottom of the pyrolysis reactor 11 and is used to discharge the generated pyrolysis carbon and waste pyrolysis catalyst. This outlet can be connected to the waste pyrolysis catalyst collection system for subsequent treatment or regeneration of the pyrolysis catalyst.

[0047] In this embodiment, the hydrogenation reactor 21 in the plasma on-line hydrogenation reaction unit 2 is coaxially arranged with the pyrolysis reactor 11. Inside the hydrogenation reactor 21, there is a cylindrical hydrogenation high-voltage electrode 211, and hydrogenation grounding electrodes 212 are respectively arranged on the outer side and the inner side of the hydrogenation reactor; its lower part is designed with a conical cavity structure 215. Due to uneven radial force, the hydrogenation catalyst rolls and sinks in the reactor, thus effectively alleviating the carbon deposition deactivation of the hydrogenation catalyst. The hydrogenation reactor 21 is also provided with a second feed port 213 (for uniformly adding hydrogenation catalyst) and a third feed port 214 (for introducing hydrogen). The hydrogenation reaction temperature in the hydrogenation reactor 21 is strictly limited to 300 - 400 °C, and is specifically set to 350 °C in this embodiment. During the reaction process, the pyrolysis gas enters the hydrogenation reactor 21 through the pyrolysis gas vent hole 115; the hydrogenation high-voltage electrode is connected to a variable-frequency high voltage, and high-voltage discharge is carried out through the hydrogenation grounding electrode and the insulating medium coated on their surfaces, and uniform hydrogen plasma is generated by dielectric barrier discharge technology to excite hydrogen; through the synergistic effect of the hydrogen plasma and the hydrogenation catalyst, the on-line catalytic hydrodeoxygenation reaction is completed to generate hydrogenation products. The hydrogenation products and waste hydrogenation catalyst are discharged from the second discharge port 216 of the hydrogenation reactor 21. Among them, the hydrogenation product outlet is connected to the subsequent condensation separation system, and the gaseous hydrogenation products are extracted and then condensed and separated to obtain liquid fuel products and non-condensable gas; while the waste hydrogenation catalyst outlet can be connected to the catalyst recovery or regeneration system to realize the centralized treatment and resource utilization of the waste hydrogenation catalyst.

[0048] In this embodiment, asFigure 1 As shown, the addition part of the hydrogenation catalyst adopts an annular catalyst inlet, and the top structure adopts a frustum shape design. Specifically, on the hydrogenation reactor 21, there is not only a second feed port 213 for adding the hydrogenation catalyst, but also an annular catalyst inlet and a frustum shape are respectively arranged on its upper part and top. This annular structure inlet facilitates the uniform addition of the hydrogenation catalyst into the hydrogenation reactor, and the frustum-shaped top structure is used to disperse the falling hydrogenation catalyst to achieve uniform distribution of the catalyst in the bed, thereby realizing efficient and uniform catalytic reactions.

[0049] In addition, as Figure 1 shown, the top end of the second discharge port 216 is connected to the bottom of the hydrogenation reactor 21. The side of the second discharge port 216 is provided with a hydrogenation product outlet, and the bottom end is provided with a spent hydrogenation catalyst outlet. In this pipeline, the solid waste hydrogenation catalyst sinks naturally in the vertical direction and is discharged, while the gaseous hydrogenation product is extracted synergistically by the fan 301 and the negative pressure system to achieve continuous and efficient discharge.

[0050] In this embodiment, the electrodes 111, 112, 211, 212 of each component are all made of high-temperature resistant metal materials and are wrapped with an insulating medium outside the electrodes to stably discharge and excite plasma, ensuring long-term stability under high-temperature and high-pressure reaction conditions. The insulating medium includes but is not limited to ceramics, quartz, etc. In this embodiment, ceramics are used.

[0051] The pyrolysis reaction temperature is strictly controlled between 400 - 500 °C, and the hydrogenation reaction temperature is controlled between 300 - 400 °C to achieve the best reaction efficiency. The spent pyrolysis catalyst discharge port 114 can be docked with the waste catalyst collection system, and the hydrogenation product outlet (through the side of the first discharge pipeline 210) can be connected to the condensation separation system to further separate and obtain liquid fuels and gaseous products.

[0052] In summary, in this embodiment, by precisely controlling the pyrolysis and hydrogenation reaction temperatures, and using metal electrodes wrapped with insulating media to ensure safe and stable operation, the on-line catalytic hydrodeoxygenation reaction of biomass pyrolysis gas is realized, and the integration and compact design of the pyrolysis and hydrogenation reactors are achieved. While saving space, the energy consumption and material loss are effectively reduced through on-line hydrogenation, providing a feasible technical path for the efficient utilization of biomass raw materials.

[0053] Through the conversion method of biomass pyrolysis and on-line hydro-upgrading of pyrolysis gas, the present invention can obtain liquid products such as pyrolysis carbon and liquid fuels, as well as three-phase products of carbon-containing non-condensable gas. Through catalyst design and the adjustment of process parameters, co-production of multiple types of target products or directional preparation of a certain type of product can be realized, achieving the high-value utilization of biomass resources.

[0054] Example 2

[0055] Example 2 provides a coaxial dual-zone plasma-coupled pyrolysis online hydrogenation method, as Figure 3 , which is applied to the above-mentioned coaxial dual-zone plasma-coupled pyrolysis online hydrogenation device and includes the following steps:

[0056] (1) Plasma-assisted biomass pyrolysis

[0057] The biomass raw material and the pyrolysis catalyst are added into the pyrolysis reactor 11 through the first feed port (pyrolysis raw material and pyrolysis catalyst inlet) 113. Under the action of the pyrolysis high-voltage electrode 111 and the pyrolysis ground electrode 112, the biomass raw material rapidly undergoes a pyrolysis reaction to generate pyrolytic carbon, waste pyrolysis catalyst, and pre-treated pyrolysis gas with reduced molecular weight. The pyrolytic carbon and the waste pyrolysis catalyst are discharged from the first discharge port 114, while the pyrolysis gas is discharged through the pyrolysis gas vent hole and directly enters the plasma online hydrogenation reaction unit.

[0058] (2) Hydrogen introduction and hydrogen plasma excitation

[0059] In the hydrogenation reactor 21, hydrogen is introduced through the third feed port 214. At the same time, the hydrogen is excited by the electric field formed between the hydrogenation high-voltage electrode 211 and the hydrogenation ground electrode 212 to generate hydrogen plasma, providing an abundant active hydrogen source for the catalytic hydrogenation reaction. At this time, the temperature in the hydrogenation reactor is controlled between 300 - 400 °C, and is specifically set to 350 °C in this example.

[0060] (3) Atmospheric pressure online catalytic hydrogenation reaction

[0061] The hydrogenation catalyst is evenly added through the second feed port 213 (and the attached circular inlet and frustum-shaped top structure) provided on the hydrogenation reactor, so that the hydrogenation catalyst is fully mixed with the hydrogen plasma and the incoming pre-treated pyrolysis gas, and the online catalytic hydrogenation reaction is realized under atmospheric pressure conditions to generate hydrogenation products and waste hydrogenation catalyst.

[0062] (4) Product discharge and separation

[0063] The hydrogenation products and the waste hydrogenation catalyst after the reaction are discharged from the second discharge port 216 of the hydrogenation reactor and discharged from the first outlet and the second outlet through the first discharge pipeline respectively; the hydrogenation product outlet is connected to a fan (301), and the hydrogenation products are continuously and stably pumped out through a negative pressure system, and the hydrogenation products are further sent to a subsequent device for condensation separation to obtain liquid and gas products.

[0064] Through the above steps, in this embodiment, by precisely controlling the pyrolysis and hydroprocessing reaction temperatures, using a metal electrode to wrap the insulating medium to ensure safe and stable operation, the on-line catalytic hydrodeoxygenation reaction of biomass pyrolysis gas is realized, and the integration and compact design of the pyrolysis and hydroprocessing reactors are achieved. While saving space, the energy consumption and material loss are effectively reduced through on-line hydrogenation, providing a feasible technical path for the efficient utilization of biomass raw materials.

[0065] Obviously, those skilled in the art can make various modifications and variations to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and its equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. Coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device, characterized in that: The device includes: The plasma-assisted pyrolysis reaction unit comprises a pyrolysis reactor, wherein a pyrolysis high-voltage electrode and a pyrolysis ground electrode are arranged inside the cavity of the pyrolysis reactor, and is used to perform a pyrolysis reaction on the biomass to generate pyrolysis char, waste pyrolysis catalyst and pre-treated pyrolysis gas, and the pre-treated pyrolysis gas is discharged through the pyrolysis gas vent; The plasma online hydrogenation reaction unit comprises a hydrogenation reactor coaxially arranged with the pyrolysis reactor, wherein a hydrogenation high-voltage electrode and a hydrogenation grounding electrode are arranged inside the cavity of the hydrogenation reactor, and are used to realize an online catalytic hydrogenation reaction on the pretreated pyrolysis gas to generate hydrogenation products and waste hydrogenation catalysts, and the hydrogenation products and the waste hydrogenation catalysts are separated and discharged through a second discharge port.

2. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1 is characterized in that: The pyrolysis reactor is connected to the hydrogenation reactor through the pyrolysis gas vent hole, and the pre-treated pyrolysis gas is directly discharged through the pyrolysis gas vent hole and enters the plasma online hydrogenation reaction unit online.

3. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1 is characterized in that: The pyrolysis high-voltage electrode is connected to the variable-frequency high-voltage electricity, and high-voltage discharge is performed with the pyrolysis ground electrode and the insulating medium coated on the surface of each other, and uniform plasma is excited by the dielectric barrier discharge technology to achieve preliminary quality improvement of the pyrolysis gas to obtain pyrolysis gas with a smaller molecular weight; the hydrogenation high-voltage electrode is connected to the variable-frequency high-voltage electricity, and high-voltage discharge is performed with the hydrogenation ground electrode and the insulating medium coated on the surface of each other, and hydrogen is excited by the dielectric barrier discharge technology to generate uniform hydrogen plasma, so as to achieve online hydrogenation quality improvement of the pretreated pyrolysis gas.

4. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1 is characterized in that: The plasma-assisted pyrolysis reaction unit is also provided with a first feed port and a first discharge port; wherein the first feed port is used to add biomass raw materials and pyrolysis catalysts, and generate pyrolysis char, waste pyrolysis catalysts and pretreated pyrolysis gas through pyrolysis reaction; the pyrolysis char and waste pyrolysis catalysts are discharged through the first discharge port.

5. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1 is characterized in that: The lower part of the hydrogenation reactor is designed as a conical cavity structure.

6. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1, characterized in that: The hydrogenation reactor is also provided with a second feed port for adding a hydrogenation catalyst; and a third feed port is also provided for introducing hydrogen required for the reaction; the second feed port is annular, and the top structure of the pyrolysis reactor is truncated cone-shaped.

7. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 1 is characterized in that: The hydrogenation high-voltage electrodes are arranged between the pyrolysis reactor and the hydrogenation reactor cavity, and are distributed in a circle with equal angles, and may be arranged in one circle or multiple circles.

8. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 5, characterized in that: It also includes a second discharge port, the top of which is connected to the bottom of the conical cavity structure of the hydrogenation reactor, a hydrogenation product outlet is arranged on the side of the second discharge port, and a waste catalyst outlet is arranged at the bottom of the second discharge port.

9. The coaxial dual-zone plasma coupled pyrolysis online hydrogenation reaction device according to claim 8, characterized in that: The hydrogenation product outlet is connected to a fan, and the hydrogenation product is stably extracted through a negative pressure system.

10. A coaxial dual-zone plasma integrated coupled pyrolysis online hydrogenation reaction method, characterized in that: The following steps are involved: (1) Plasma-assisted biomass pyrolysis The biomass raw material and the pyrolysis catalyst are added into the pyrolysis reactor through the first feed port, and the biomass undergoes a pyrolysis reaction under the action of the pyrolysis high-voltage electrode and the pyrolysis ground electrode to generate pyrolysis char, waste pyrolysis catalyst and pre-treated pyrolysis gas with reduced molecular weight; the pyrolysis char and the waste pyrolysis catalyst are discharged from the first discharge port, and the pyrolysis gas is discharged through the pyrolysis gas vent and directly enters the plasma online hydrogenation reaction unit; (2) Hydrogen introduction and hydrogen plasma excitation In the hydrogenation reactor, hydrogen is introduced through the third feed port, and the hydrogen is excited by the electric field formed between the hydrogenation high-voltage electrode and the hydrogenation ground electrode to generate hydrogen plasma; (3) Atmospheric pressure online catalytic hydrogenation reaction The hydrogenation catalyst is uniformly added through the second feed port provided on the hydrogenation reactor, so that the hydrogenation catalyst is fully mixed with the hydrogen plasma and the introduced pre-treated pyrolysis gas, and an online catalytic hydrogenation reaction is realized under normal pressure conditions to generate hydrogenation products and spent hydrogenation catalyst; (4) Product discharge and separation The hydrogenation product after the reaction and the spent hydrogenation catalyst are discharged through the second discharge port through the spent catalyst outlet and the hydrogenation product outlet of the hydrogenation reactor respectively; the hydrogenation product outlet is connected to the fan, and the hydrogenation product is continuously and stably extracted through the negative pressure system. The hydrogenation product is further sent to the subsequent device for condensation separation to obtain liquid and gas products.

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