Renewable energy driven biomass pyrolysis-gas phase hydrogenation upgrading system and method

Abstract

The invention relates to the technical field of biomass recycling, and particularly discloses a renewable energy driven biomass pyrolysis-gas phase hydrogenation upgrading system and method.The system comprises a solar heat collection system, a catalytic pyrolysis system, a plasma hydrogenation system and a condensation system. The solar heat collection system uses sunlight to heat a heat storage medium, the catalytic pyrolysis system is used for biomass catalytic pyrolysis to generate pyrolysis gas and carbon, the plasma hydrogenation system is used for exciting green hydrogen through green electricity to generate hydrogen plasma to perform catalytic hydrogenation on the pyrolysis gas, and the condensation system is used for condensing hydrogenation products to obtain liquid fuel. Biomass pyrolysis-gas phase hydrogenation driven by solar thermal driving and renewable green electricity can be achieved, online catalytic hydrogenation is achieved through active hydrogen plasma and pyrolysis gas, compared with a traditional process, stable consumption of renewable green electricity and green hydrogen can be achieved, the whole process is low in carbon emission, small in loss and low in energy consumption, and the method is suitable for industrial production. And the operation is safer and more stable under lower pressure.

Description

Technical Field

[0001] This application relates to the technical field of biomass resource utilization, and particularly to a biomass pyrolysis-gas phase hydro-upgrading system and method driven by renewable energy. Background Art

[0002] At present, China is in a critical stage of replacing fossil energy with renewable energy. How to achieve the stable consumption and long-term energy storage of a large amount of renewable energy (including renewable energy derivatives such as green electricity and green hydrogen) is an urgent problem to be solved. Biomass is the only carbon-containing renewable resource mainly composed of holocellulose and lignin, which can be catalytically converted and upgraded to prepare three-phase products such as oil, gas, and carbon. Using biomass as an energy carrier and driving the conversion of biomass with renewable energy such as wind, light, water and their derived green hydrogen and green electricity, and further converting renewable energy into chemical energy in high-value biomass-based energy products is an effective way for stable consumption. The gas-phase volatile matter in biomass pyrolysis is rich in oxygen-containing unsaturated components, and high-quality hydrocarbon liquid fuels such as aromatics and alkanes can be prepared through hydrodeoxygenation reactions, which are one of the important energy materials urgently needed in China at present.

[0003] However, the traditional biomass thermochemical process for preparing high-quality hydrocarbon liquid fuels usually condenses the biomass pyrolysis products, and then transfers the condensed bio-oil to a hydrothermal reaction system for product synthesis. The hydrothermal process is a mixed reaction process of bio-oil, catalyst and water or organic solvent, and often further operations such as condensation, filtration, fractionation, and extraction are required. The energy consumption of the condensation and reheating process is high, and the hydrothermal reaction hydrogenation process usually requires a pressure of several MPa to more than a dozen MPa. Therefore, the traditional process has high carbon emissions, a long process, large losses, and a high degree of danger. Summary of the Invention

[0004] In order to achieve the efficient consumption of renewable energy while preparing high-quality biomass-based energy products, this application provides a biomass pyrolysis-gas phase hydro-upgrading system and method driven by renewable energy.

[0005] A biomass pyrolysis-gas phase hydro-upgrading system driven by renewable energy provided by this application adopts the following technical solutions: A biomass pyrolysis-gas phase hydro-upgrading system driven by renewable energy, comprising: A solar thermal collection system that uses sunlight to heat a heat storage medium; The catalytic pyrolysis system includes a pyrolysis reactor, which has a downward moving bed structure and is rotatably provided with a double spiral ribbon agitator; a plurality of heat storage medium flow pipes are also rotatably arranged in the pyrolysis reactor, and spiral fins are arranged on the outer periphery of the heat storage medium flow pipes; the heat storage medium heated by the solar heat collection system flows in the heat storage medium flow pipes to supply heat for the biomass pyrolysis reaction in the pyrolysis reactor. The plasma hydrogenation system includes a hydrogenation reactor for catalytic hydrodeoxygenation of the pyrolysis gas generated by the pyrolysis reactor through hydrogen plasma and a catalyst. The condensation system is used for condensing the hydrogenation products of the plasma hydrogenation system.

[0006] Furthermore, the agitator is arranged at the center of the pyrolysis reactor, and a plurality of the heat storage medium flow pipes are equiangular and concentrically distributed in the pyrolysis reactor.

[0007] The pyrolysis reactor in this application has a downward moving bed structure. Compared with the traditional fluidized bed, it has a simple structure, is easy to maintain, and greatly reduces the required gas carrier volume. However, since the overall heat and mass transfer efficiency of the downward moving bed is lower than that of the fluidized bed, a stirring device usually needs to be set. The unique structure of the double spiral ribbon agitator can not only radially mix and drive the surrounding bed materials downward, but also lift the bed materials at the bottom along the double spiral ribbon and scatter them around in the reverse direction. Therefore, it can realize multi-dimensional stirring of the bed materials in the axial and radial directions in the reactor. In order to make the double spiral ribbon agitator compatible with the heat storage medium flow pipes, the double spiral ribbon agitator is arranged at the center of the pyrolysis reactor, and a plurality of heat storage medium flow pipes are arranged around the double spiral ribbon agitator. Conventional heat storage medium flow pipes are fixedly arranged, resulting in the bed materials around the heat storage medium flow pipes being difficult to be stirred. Therefore, in this application, spiral fins are arranged on the outer periphery of the heat storage medium flow pipes, and the heat storage medium flow pipes are rotatably arranged. On the one hand, the spiral fins increase the heat exchange contact area and improve the heat transfer efficiency. On the other hand, they can realize the stirring of the bed materials around the heat storage medium flow pipes and improve the overall mixing efficiency of the bed materials.

[0008] Furthermore, the agitator and the heat storage medium flow pipes rotate in opposite directions.

[0009] This helps to improve the stability of stirring.

[0010] Furthermore, the solar heat collection system includes a condenser, a heat storage tower, and a buffer tank. The condenser is used to collect and reflect sunlight onto the heating chamber at the top of the heat storage tower. The heating chamber is used to receive the concentrated sunlight and heat the heat storage medium. The heating chamber is connected to the heat storage medium flow pipes, and the buffer tank is used for supplementing or removing the heat storage medium.

[0011] Further, the catalytic pyrolysis system further includes a screw feeder, a solid sieve, a carbon storage bin, and a pyrolysis catalyst regeneration reactor. The screw feeder is used to feed biomass raw materials into the pyrolysis reactor. The solid sieve is used to separate the mixture of waste catalysts and biochar discharged from the reactor. The carbon storage bin is used to store the sieved biochar. The pyrolysis catalyst regeneration reactor is used to regenerate the sieved waste pyrolysis catalysts.

[0012] Further, the plasma hydrogenation system further includes a hydrogenation catalyst regeneration reactor for regenerating waste hydrogenation catalysts.

[0013] Further, the hydrogenation products generated by the hydrogenation reactor are divided into a first part and a second part. The first part enters the condensation system, and the second part enters the hydrogenation reactor for cyclic hydrogenation.

[0014] Further, a pyrolysis catalyst regeneration system is also included. The pyrolysis catalyst regeneration system includes a pyrolysis catalyst regeneration reactor for removing carbon deposits on waste pyrolysis catalysts to generate regenerated pyrolysis catalysts and re-inputting the regenerated pyrolysis catalysts into the pyrolysis reactor.

[0015] This application also provides a biomass pyrolysis-gas phase hydrogenation upgrading method driven by renewable energy, including the following steps: Solar concentrating heat collection: Using sunlight to heat the heat storage medium and introducing the heated heat storage medium into the heat storage medium pipeline; Biomass catalytic pyrolysis: Inputting dry biomass raw materials, catalysts, and carrier gas into the pyrolysis reactor, and realizing biomass catalytic pyrolysis through the cooperation of three heating methods, namely, electric heating, heating by the heat storage medium pipeline, and heating by the regenerated pyrolysis catalyst, so that the biomass pyrolysis generates pyrolysis gas and pyrolysis carbon; Online hydrogenation of pyrolysis gas: Introducing pyrolysis gas into the hydrogenation reactor and adding a catalyst, introducing hydrogen into the plasma excitation device to generate hydrogen plasma, and catalytically hydrogenating and deoxidizing the pyrolysis gas through the hydrogen plasma and the catalyst to generate hydrogenation products; Product condensation and separation: The hydrogenation products enter the condensation system, and after condensation, a condensed liquid product and a non-condensable gas are obtained respectively.

[0016] Further, in the biomass catalytic pyrolysis step, the double spiral ribbon stirring paddle and the heat storage medium flow pipeline with spiral fins on the outside are stirred simultaneously to achieve full mixing of the bed material and downward driving.

[0017] In summary, this application includes at least one of the following beneficial technical effects: This application combines solar thermal-assisted heating, green-electricity-driven electric heating, and electro-excited plasma technology to achieve online upgrading of biomass pyrolysis driven by renewable energy. It uses hydrogen plasma generated by green hydrogen excitation instead of conventional hydrogen as the reaction hydrogen source to achieve hydrodeoxygenation of biomass pyrolysis gas in a low-pressure gas phase, solving the problems of long process flow, large losses, and high energy consumption in the traditional process of condensing biomass pyrolysis products into bio-oil and then further realizing hydrodeoxygenation to prepare liquid fuels through a high-pressure hydrogenation system. While preparing high-quality biomass-based energy products, it also realizes efficient consumption of renewable energy. At the same time, the online reaction is easy to control, facilitating the integration of multiple reactions and the design of a compact reactor.

[0018] By setting a rotating heat storage medium flow pipe with a spiral fin structure on the outside in the pyrolysis reactor, on the one hand, it increases the heat transfer contact area to improve the heat transfer efficiency, and on the other hand, it can stir the bed material around the heat storage medium flow pipe to improve the overall mixing efficiency of the bed material. Description of the Drawings

[0019] Figure 1 is the overall structural schematic diagram of a renewable energy-driven biomass pyrolysis-gas phase hydro-upgrading system according to an embodiment of the present application; Figure 2 is the equipment structural schematic diagram of a renewable energy-driven biomass pyrolysis-gas phase hydro-upgrading system according to an embodiment of the present application; Figure 3 is the internal structural schematic diagram of the pyrolysis reactor in a renewable energy-driven biomass pyrolysis-gas phase hydro-upgrading system according to an embodiment of the present application, where (a) is a three-dimensional view and (b) is a top view; Figure 4 is the flow chart of a renewable energy-driven biomass pyrolysis-gas phase hydro-upgrading method according to an embodiment of the present application.

[0020] Reference Numerals: 1. Pyrolysis Reactor; 101. Pyrolysis Carrier Gas Inlet; 102. Heat Storage Medium Inlet; 103. Regenerated Pyrolysis Catalyst Inlet; 104. Stirring Device; 105. Pyrolysis Raw Material Inlet; 106. Heat Storage Medium Outlet; 107. Pyrolysis Product Outlet; 108. Heat Storage Medium Flow Pipe; 109. Double-Screw Rib Stirring Paddle; 110. Discharger; 111. Pyrolysis Gas Discharge Port; 112. Heat Storage Medium Inflow Pipe; 113. Regenerated Pyrolysis Catalyst Inflow Pipe; 114. Pyrolysis Solid Reaction Material Inflow Pipe; 115. Pyrolysis Gas Discharge Pipe; 116. Heat Storage Medium Discharge Pipe; 117. First Compression Pump; 2. Screw Feeder; 201. Silo; 202. Feeding Port; 203. Discharge Port; 3. Solid sieve; 301. Pyrolysis solid inlet; 302. Sieve mesh; 303. Spent pyrolysis catalyst outlet; 304. Biochar discharge pipe; 305. Spent pyrolysis catalyst discharge pipe; 4. Biochar storage bin; 401. Biochar inlet; 402. Biochar outlet; 5. Pyrolysis catalyst regeneration reactor; 501. Spent pyrolysis catalyst inlet; 502. First hot air inlet; 503. First hot flue gas outlet; 504. Regenerated pyrolysis catalyst outlet; 505. Regenerated pyrolysis catalyst three-way valve; 6. Hydrogenation reactor; 601. Pyrolysis gas inlet; 602. Catalyst inlet; 603. Hydrogen inlet; 604. Plasma torch; 605. Regenerated hydrogenation catalyst inlet; 606. Plasma nozzle; 607. Hydrogenation reactor discharge port; 608. Hydrogenation product outlet; 609. Circulating hydrogenation product outlet; 610. Second compression pump; 611. Circulating hydrogenation product inlet; 612. Spent hydrogenation catalyst outflow pipe; 613. First discharge pipe; 614. Second discharge pipe; 615. Regenerated hydrogenation catalyst inflow pipe; 7. Hydrogenation catalyst regeneration reactor; 701. Spent hydrogenation catalyst inlet; 702. Second hot air inlet; 703. Second hot flue gas outlet; 704. Regenerated hydrogenation catalyst outlet; 705. Regenerated hydrogenation catalyst three-way valve; 8. Condenser; 801. Hydrogenation product inlet; 802. Non-condensable gas outlet; 803. Condensed liquid product outlet; 9. Heat storage tower; 901. Heating bin; 902. Heating bin discharge port; 903. Heat storage medium lifting pipe; 904. Peristaltic pump; 905. Heat storage medium inlet; 906. Heat storage medium buffer tank; 907. Heat storage medium supplement port; 908. Heat storage medium discharge port; 10. Condensing lens. Detailed implementation mode

[0021] The following is a further detailed description of this application in combination with the attached Figures 1-4 to this application.

[0022] Example 1 In related technologies, in the traditional biomass thermochemical preparation process of high-quality liquid fuels, grey hydrogen and blue hydrogen are mainly used in terms of hydrogen sources. Technologically, the pyrolysis products of biomass are mainly condensed, and then the condensed bio-oil is transferred to a hydrothermal reaction system for synthesis. The hydrothermal process is a mixed reaction process of bio-oil, catalyst, and water or organic solvents, and often further operations such as condensation, filtration, fractionation, and extraction are required. The condensation and reheating processes have high energy consumption, and the hydrogenation process in the hydrothermal reaction usually requires a pressure of several megapascals to more than a dozen megapascals. Therefore, the traditional process has high carbon emissions, a long process, large losses, and a relatively high degree of danger.

[0023] Example 1 provides a biomass pyrolysis-gas phase hydro-upgrading system driven by renewable energy. The catalytic pyrolysis reaction of biomass is carried out by the solar photothermal-assisted heating of the pyrolysis reactor 1 to produce pyrolysis gas. Then, the pyrolysis gas is subjected to an on-line catalytic hydrodeoxygenation reaction using a hydrogenation catalyst and hydrogen plasma in the hydrogenation reactor 6, so that the pyrolysis gas generates hydrogenation products. Then, the hydrogenation products are condensed by the condenser 8 to obtain a condensed liquid product and non-condensable gas. Thus, on-line catalytic hydrogenation in the gas phase driven by renewable energy can be realized. The hydrogen plasma generated by exciting green hydrogen is used as the reaction hydrogen source to carry out a catalytic hydrogenation reaction with the gas phase pyrolysis products, which can reduce the carbon emissions of the overall process, and the overall losses and energy consumption are lower. Moreover, the operation at a lower pressure is safer.

[0024] Example 1 provides a biomass pyrolysis-gas phase hydro-upgrading system driven by renewable energy, as Figure 1 and 2 shown, including a catalytic solar photothermal system, a catalytic pyrolysis system, a plasma hydrogenation system and a condensation system.

[0025] The solar photothermal system includes a heat storage tower 9 and a concentrator 10. A heating chamber 901 is arranged at the top of the heat storage tower. The discharge port 902 of the heating chamber is connected to the heat storage medium flow pipeline 108 in the pyrolysis reactor 1 through the heat storage medium inflow pipeline 112. A heat storage medium lifting pipeline 903 is arranged inside the heat storage tower, and a peristaltic pump 904 is provided thereon to provide the upward driving force of the heat storage medium. The heat storage medium inlet 905 at the bottom of the heat storage medium lifting pipeline 903 is connected to the heat storage medium flow pipeline 108 in the pyrolysis reactor 1 through the heat storage medium discharge pipeline 116. A heat storage medium buffer tank 906 is also arranged on the heat storage medium discharge pipeline 116 to supplement or discharge the heat storage medium.

[0026] The catalytic pyrolysis system includes a pyrolysis reactor 1 and a pyrolysis carrier gas inlet 101, a heat storage medium inlet 102, a regenerated pyrolysis catalyst inlet 103, a stirring device 104, a pyrolysis raw material inlet 105, a heat storage medium outlet 106, and a pyrolysis product outlet 107 arranged on the pyrolysis reactor 1. The pyrolysis reactor 1 is of a downward moving bed structure, and a heat storage medium flow pipeline 108 is arranged inside it. A double spiral ribbon stirring paddle 109 is arranged on the stirring device 104. The bottom of the pyrolysis reactor 1 is connected to a solid sieve 3 and a carbon storage bin 4. The pyrolysis reactor 1 is used to carry out a pyrolysis reaction on biomass to produce pyrolysis gas and pyrolysis carbon. The pyrolysis gas is discharged through the pyrolysis gas discharge pipeline 115, and the pyrolysis carbon and the waste pyrolysis catalyst are discharged from the pyrolysis product outlet 107.

[0027] The plasma hydrogenation system includes a hydrogenation reactor 6, on which there are a hydrogenation reactant inlet 601, a catalyst inlet 602, a hydrogen plasma excitation device 604 and a hydrogenation reactor discharge outlet 607. The hydrogenation reactant inlet 601 is connected to the pyrolysis gas discharge outlet 111 through a pyrolysis gas discharge pipeline 115. A first compression pump 117 is provided on the pyrolysis gas discharge pipeline 115. The pyrolysis gas enters the hydrogenation reactor 6 from the hydrogenation reactant inlet 601 through the pyrolysis gas discharge pipeline 115. The catalyst inlet 602 is used to add a new hydrogenation catalyst. The hydrogen plasma excitation device 604 is used to generate hydrogen plasma. The hydrogenation reactor 6 catalyzes and hydrogenates the pyrolysis gas through the hydrogen plasma and the hydrogenation catalyst to generate a hydrogenation product. The hydrogenation product outlet 608 is used to discharge the hydrogenation product.

[0028] The condensation system includes a condenser 8, on which there are a hydrogenation product inlet 801, a condensed liquid product outlet 803 and a non-condensable gas outlet 802. The hydrogenation product inlet 801 is communicated with the hydrogenation product outlet 608. The hydrogenation product enters the condenser 8 through the hydrogenation product inlet 801. The condenser 8 is used to condense the hydrogenation product to obtain a condensed liquid product and a non-condensable gas. The condensed liquid product outlet 803 is used to discharge the condensed liquid product. The non-condensable gas outlet 802 is used to discharge the non-condensable gas.

[0029] A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy provided in this embodiment uses a plasma excitation device to excite green hydrogen to generate hydrogen plasma as a reaction hydrogen source, and realizes the hydrodeoxygenation of biomass pyrolysis gas in a gas phase at a relatively low pressure slightly higher than atmospheric pressure of 0.1-0.2 MPa, solving the problems of high carbon emissions, long process flow, large losses and high energy consumption in the process of condensing biomass pyrolysis gas into bio-oil and then further realizing hydrodeoxygenation to prepare liquid fuel through a high-pressure hydrogenation system. At the same time, the on-line reaction is easy to control, which is convenient for realizing multi-reaction integration.

[0030] In this embodiment, as Figure 1 and 2 shown, a peristaltic pump 904 is provided on the heat storage medium lifting pipeline 903 inside the heat storage tower to control the overall flow of the heat storage medium. The heat storage medium, including but not limited to water / steam, hot sand particles, molten salt, heat transfer oil, liquid metal, etc., can be specifically selected according to the specific use scenario, and this embodiment does not limit this. In the specific implementation manner of this embodiment, the heat storage medium is molten salt.

[0031] In this embodiment, as Figure 1 and 2As shown in the figure, the pyrolysis raw material inlet 105 is arranged at the top of the pyrolysis reactor 1 and is used to add biomass raw materials or a mixture of raw materials and catalysts. The biomass raw materials include but are not limited to straw, rice straw, wood chips, rice husks, etc., and this embodiment does not limit this. In the specific implementation manner of this embodiment, the biomass raw material 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. The heat in the pyrolysis reactor 1 is supplied jointly by three methods, namely, electric heating, heating by the heat storage medium flow pipeline 108, and heating by the regenerated pyrolysis catalyst. The carrier gas inlet 101 is arranged on the side of the pyrolysis reactor 1 and is used to add an inert carrier gas, usually nitrogen, argon, etc. or the pyrolysis tail gas available in industry. The pyrolysis product outlet 107 is arranged at the bottom of the pyrolysis reactor 1 and is used to discharge the pyrolysis gas, pyrolysis carbon, and waste pyrolysis catalyst after the reaction.

[0032] As Figure 2 and Figure 3 shown, the double - helix ribbon stirring paddle 109 is rotatably arranged at the center of the pyrolysis reactor 1, and the heat storage medium flow pipeline 108 is rotatably arranged in the pyrolysis reactor 1, and a plurality of heat storage medium flow pipelines 108 are equally - angled and co - circularly distributed in the pyrolysis reactor. The outer periphery of the heat storage medium flow pipeline 108 is provided with spiral fins, and the rotation direction of the double - helix ribbon stirring paddle 109 is opposite to that of the heat storage medium flow pipeline 108.

[0033] In this embodiment, as Figure 1 and 2 shown, it further includes a pyrolysis catalyst regeneration system, including a pyrolysis catalyst regenerator 5 and the waste pyrolysis catalyst inlet 501, the first air inlet 502, the first hot flue gas outlet 503, the regenerated pyrolysis catalyst outlet 504, and the regenerated pyrolysis catalyst three - way valve 505 arranged thereon. The waste pyrolysis catalyst inlet 501 is connected to the waste pyrolysis catalyst discharge pipeline 305 so that the waste pyrolysis catalyst can be discharged into the pyrolysis catalyst regeneration reactor 5. The waste pyrolysis catalyst discharge pipeline 305 is inclined at a certain angle to facilitate the waste pyrolysis catalyst to slide into the pyrolysis catalyst regeneration reactor 5. The pyrolysis catalyst regeneration reactor 5 is used to remove the carbon deposition on the waste pyrolysis catalyst to generate the regenerated pyrolysis catalyst.

[0034] Specifically, as Figure 1 and 2 shown, the pyrolysis catalyst regeneration reactor 5 is provided with the first air inlet 502, the first hot flue gas outlet 503, and the regenerated pyrolysis catalyst outlet 504. The first air inlet 502 is used to introduce fresh air, the regenerated pyrolysis catalyst outlet 504 is used to discharge the regenerated pyrolysis catalyst, and the first hot flue gas outlet 503 is used to discharge the hot flue gas.

[0035] In this embodiment, as Figure 1 and2 As shown, the outlet 504 of the regenerative pyrolysis catalyst is connected to one end of the regenerative pyrolysis catalyst three-way valve 505 through a heat-insulating pipeline. The other end of the regenerative pyrolysis catalyst three-way valve 505 is connected to the inlet 103 of the regenerative pyrolysis catalyst through the regenerative pyrolysis catalyst inflow pipeline 113. The third end is used to discharge the regenerative pyrolysis catalyst from the system.

[0036] In this embodiment, the regenerative pyrolysis catalyst inflow pipeline 113 is a heat-insulating pipeline to ensure that the regenerative pyrolysis catalyst inflow pipeline 113 keeps the regenerative pyrolysis catalyst warm.

[0037] In this embodiment, as Figure 1 and 2 shown, the hydrogen plasma excitation device is a plasma torch 604. A hydrogen inlet 603 and a plasma nozzle 606 are arranged on the plasma torch 604. The hydrogen inlet 603 is used to introduce hydrogen. The hydrogen includes but is not limited to gray hydrogen, blue hydrogen, green hydrogen, etc. In the specific implementation manner of this embodiment, green hydrogen generated from renewable energy is used as the hydrogen source. The plasma nozzle 606 is arranged at the top of the inner cavity of the hydrogenation reactor 6 to spray hydrogen plasma into the hydrogenation reactor 6. The plasma torch 604 can be directly powered by the power grid or powered by renewable green electricity such as wind power, photovoltaic power, and hydropower for on-site consumption. In the specific implementation manner of this embodiment, the plasma torch 604 is driven by green electricity.

[0038] In this embodiment, as Figure 1 and 2 shown, the hydrogenation reactor 6 includes a columnar cavity and a conical cavity arranged from top to bottom. By arranging a conical cavity at the lower part of the hydrogenation reactor 6, due to different radial forces, the catalyst will roll and sink in the reactor cavity, which helps to reduce coking. In addition, spiral guide grooves can be arranged on the inner wall surface of the conical cavity to provide a path for the catalyst to roll and extend the contact time between the reactants and the catalyst, so as to improve the reaction efficiency.

[0039] In this embodiment, the pyrolysis gas discharge pipeline 115, the first discharge pipeline 613, and the second discharge pipeline 614 are all heat-insulating pipelines. The pyrolysis gas is kept warm by the pyrolysis gas discharge pipeline 115 to prevent polymerization, and the hydrogenation products are kept warm by the first discharge pipeline 613 and the second discharge pipeline 614 to prevent condensation.

[0040] In this embodiment, as Figure 1 and 2As shown, the catalyst inlet 602 is provided at the top of the columnar cavity for introducing fresh hydrogenation catalyst. The types of catalysts added through the catalyst inlet include, but are not limited to, metal oxide catalysts, zeolite molecular sieve catalysts, etc. Specifically, different types of catalysts can be selected according to the requirements of the target product. The hydrogenation reactant inlet 601 is provided on the side of the columnar cavity, the hydrogenation reactor discharge outlet 607 is provided at the bottom of the conical cavity, and the hydrogenation product outlet 608 is used to discharge the hydrogenation product.

[0041] In this embodiment, as Figure 1 and 2 shown, the hydrogenation reactor discharge outlet 607 is provided at the bottom of the hydrogenation reactor 6. Specifically, the hydrogenation reactor discharge outlet 607 is provided at the bottom of the conical cavity for discharging the hydrogenation product and the spent hydrogenation catalyst.

[0042] Specifically, in this embodiment, as Figure 1 and 2 shown, it further includes a spent hydrogenation catalyst discharge pipe 612. The top end of the spent hydrogenation catalyst discharge pipe 612 is connected to the hydrogenation reactor discharge outlet 607. A hydrogenation product outlet 609 is provided on the side of the spent hydrogenation catalyst discharge pipe 612. The spent hydrogenation catalyst sinks and is discharged into the hydrogenation catalyst regeneration reactor 7 along the spent hydrogenation catalyst discharge pipe 612. The hydrogenation product (gaseous state) is extracted through the side of the spent hydrogenation catalyst discharge pipe 612 via the screened hydrogenation product outlet 608.

[0043] In this embodiment, as Figure 1 and 2 shown, it further includes a first discharge pipe 613 and a second discharge pipe 614. The hydrogenation product is divided into a first part and a second part. One end of the first discharge pipe 613 is connected to the hydrogenation product outlet 608, and the other end is connected to the hydrogenation product inlet 801 to discharge the first part of the hydrogenation product into the condenser 8. A recycle gas outlet 609 is provided on the first discharge pipe 613, and a recycle gas inlet 611 is provided on the pyrolysis gas discharge pipe 115. One end of the second discharge pipe 614 is connected to the recycle gas outlet 609, and the other end is connected to the recycle gas inlet 611 to make the second part of the hydrogenation product enter the hydrogenation reactor 6 for cyclic hydrogenation.

[0044] Through the way of bypass reflux circulation, this application can recycle part of the hydrogenation product back to the hydrogenation reactor 6 to achieve secondary or multiple hydrogenations, and carry out cyclic hydrogenation reaction on the pyrolysis gas that was not completely reacted for the first time, thereby improving the overall conversion rate.

[0045] In this embodiment, as Figure 1 and 2As shown, a second compression pump 610 is provided on the second discharge pipeline 614. The second compression pump 610 is used to extract the second part of the hydrogenation product and perform cyclic hydrogenation by extracting the second part of the hydrogenation product.

[0046] In this embodiment, the ratio of hydrogenation product condensation to circulation is controlled by the power of the second compression pump 610, and the circulation flow rate flowing through the circulation pump does not exceed 80% of the volume flow rate of the hydrogenation product flowing out of the hydrogenation product outlet 608.

[0047] In this embodiment, as Figure 1 and 2 shown, it further includes a hydrogenation catalyst regeneration system, including a hydrogenation catalyst regeneration reactor 7 and a waste hydrogenation catalyst inlet 701, a second air inlet 702, a second hot flue gas outlet 703, a regenerated hydrogenation catalyst outlet 704 and a regenerated hydrogenation catalyst three-way valve 705 provided thereon. The waste hydrogenation catalyst inlet 701 is connected to the waste hydrogenation catalyst discharge pipeline 612 to discharge the waste hydrogenation catalyst into the hydrogenation catalyst regeneration reactor 7. The lower half of the waste hydrogenation catalyst discharge pipeline 612 is inclined at a certain angle to facilitate the waste hydrogenation catalyst to slide into the hydrogenation catalyst regeneration reactor 7. The hydrogenation catalyst regeneration reactor 7 is used to remove the carbon deposits on the waste hydrogenation catalyst to generate regenerated hydrogenation catalyst.

[0048] Specifically, as Figure 1 and 2 shown, a second air inlet 702, a second hot flue gas outlet 703 and a regenerated hydrogenation catalyst outlet 704 are provided on the hydrogenation catalyst regeneration reactor 7. The second air inlet 702 is used to introduce fresh air, the regenerated hydrogenation catalyst outlet 704 is used to discharge the regenerated hydrogenation catalyst, and the second hot flue gas outlet 703 is used to discharge the hot flue gas.

[0049] In this embodiment, as Figure 1 and 2 shown, it further includes a regenerated hydrogenation catalyst three-way valve 705. A discharge port 704 is provided at the bottom of the rear end of the hydrogenation catalyst regeneration reactor 7 and is connected to one end of the regenerated hydrogenation catalyst three-way valve 705 through a heat-insulating pipeline. The other end of the regenerated hydrogenation catalyst three-way valve 705 is connected to the regenerated hydrogenation catalyst inlet 605 through the regenerated hydrogenation catalyst inflow pipeline 615, and the third end is used to discharge the regenerated hydrogenation catalyst from the system.

[0050] In this embodiment, the regenerated hydrogenation catalyst inflow pipeline 615 is a heat-insulating pipeline to ensure heat preservation of the first part of the regenerated hydrogenation catalyst in the regenerated hydrogenation catalyst inflow pipeline 615.

[0051] In this embodiment, both the liquid condensation product and the non-condensable gas are effective products. The pyrolytic carbon can be used to prepare carbon materials including but not limited to carbon fertilizers, activated carbon, carbon electrodes, etc. The liquid condensation product includes one or more of aromatic hydrocarbons, alkanes, and alkenes depending on the catalyst used. The non-condensable gas mainly consists of CO2, CO, and a small amount of light hydrocarbons, and can be used as gas fuel or chemical raw materials, etc. in the future.

[0052] In this embodiment, both the pyrolysis catalyst regeneration reactor 5 and the hydrogenation catalyst regeneration reactor 7 have a structure similar to a riser followed by a cyclone separator. By introducing air for combustion reaction and carrying the particles upward, the carbon deposition on the spent catalyst is eliminated by combustion. Most of the heat generated by combustion enters the pyrolysis reactor 1 and the hydrogenation reactor 6 after being separated by the cyclone separator by the hot catalyst particles to supply the reaction heat.

[0053] In this embodiment, the pyrolysis catalyst is an iron-nickel bimetal supported granular catalyst with ZSM-5 as the carrier, and the hydrogenation catalyst is a nickel-molybdenum bimetal supported granular catalyst with titanium oxide as the carrier. The granular catalyst can roll and fall in the reactor.

[0054] In this embodiment, the temperature of on-line catalytic hydrodeoxygenation in the hydrogenation reactor 6 is 300-600 °C, and the heat is supplied by the heat generated by the combustion in the hydrogenation catalyst regeneration reactor 7 through the recycled hydrogenation catalyst.

[0055] In this embodiment, in order to improve the hydrogenation reaction efficiency, the hydrogenation reactor 6 operates at a relatively low pressure slightly higher than atmospheric pressure of 0.1-0.2 MPa. The pressure is mainly controlled by the flow rates of the first compression pump 117 and the second compression pump 610 and the pressure-resistant valves on the pipeline. The specific hydrogenation pressure in this embodiment is 0.15 MPa.

[0056] In summary, in this application, the plasma torch 604 is used to excite green hydrogen to generate high-energy active hydrogen plasma, and hydrodeoxygenation of biomass pyrolysis gas is realized in the gas phase, solving the problems of long process flow, large losses, and high energy consumption in the process of hydrodeoxygenation to prepare liquid fuel in the current high-pressure hydrogenation system after condensing biomass pyrolysis gas into bio-oil. At the same time, the on-line reaction is easy to control, facilitating the integration of multiple reactions and easy to design a compact reactor.

[0057] The present application can achieve the utilization efficiency of the catalyst through the reactor structure design. Among them, the lower part of the hydrogenation reactor 6 adopts a conical or pyramidal structure with an inclined angle, which can enable the catalyst to roll and sink in the reactor, thereby alleviating the problem of catalyst carbon deposition deactivation. The pyrolysis catalyst regeneration reactor 5 and the hydrogenation catalyst reactor 7 adopt a riser pipe connected to a cyclone separator structure, which can achieve the elimination of carbon deposition on the waste catalyst through combustion and carry out drying and separation. The separated catalyst particles can be continuously put into the pyrolysis reactor 1 and the hydrogenation reactor 6 for recycling.

[0058] Through the way of bypass reflux circulation, the present application can recycle part of the hydrogenation products back to the hydrogenation reactor 6 to achieve secondary or multiple hydrogenation, and can recycle the pyrolysis gas that has not fully reacted for the first time for hydrogenation reaction, thereby improving the overall conversion rate. In addition, by means of riser combustion to realize the cyclic regeneration of pyrolysis and hydrogenation catalysts, the catalyst can be recycled, the consumption of new catalysts can be reduced, and the overall process economy can be improved.

[0059] The present application realizes the heat self-supply of the biomass pyrolysis reactor 1 through solar thermal, electric heating, and reheating of the regenerated pyrolysis catalyst, and the heat supply for the hydrogenation reactor 6 during the hydrogenation catalyst regeneration process, without external heat supply, achieving the heat self-supply of the entire process.

[0060] The electric heating part and the plasma torch 604 in the pyrolysis reactor 1 used in the present application can not only be powered by the power grid, but also be driven by renewable green electricity such as wind power, photovoltaic power, and hydropower, realizing the immediate local consumption of renewable green electricity and solving the instability of renewable green electricity. On the other hand, the hydrogen source of the plasma torch 604 can not only use blue hydrogen and gray hydrogen, but also use green hydrogen generated by renewable energy, further realizing the clean and low-carbon of the overall process.

[0061] Through the conversion method of biomass pyrolysis and online hydrogenation upgrading of pyrolysis gas, the present application can obtain liquid products such as pyrolysis carbon and liquid fuel, as well as three-phase products such as carbon-containing non-condensable gas. Through catalyst design and the adjustment of process parameters, the co-production of multiple types of target products or the directional preparation of a certain type of product can be realized, achieving the high-value utilization of biomass resources.

[0062] By setting a rotating heat storage medium flow pipe and spiral fins in the pyrolysis reactor, the present application can, on the one hand, increase the heat transfer contact area to improve the heat transfer efficiency, and on the other hand, can realize the stirring of the bed material around the heat storage medium flow pipe, improving the overall mixing efficiency of the bed material.

[0063] Example 2 Example 2 provides a renewable energy-driven biomass pyrolysis-gas phase hydrogenation upgrading method, as Figure 3As shown, the following steps are included for the biomass pyrolysis-gas phase hydrogenation upgrading system driven by the above renewable energy: S1: Solar energy concentrating and heat collection: Adjust the light alignment angle of the condenser 10 to concentrate light on the heating chamber 901 at the top of the heat storage tower, heat the heat storage medium therein, start the peristaltic pump 904, and control the circulating flow of the heat storage medium; S2: Biomass catalytic pyrolysis: Input the dried biomass raw material, catalyst, and dried carrier gas into the pyrolysis reactor 1. Through the cooperation of three heat supply methods, namely, electric heating, heating by the heat storage medium flow pipe 108, and heating by the regenerated pyrolysis catalyst, biomass catalytic pyrolysis is achieved, enabling the biomass to pyrolyze to produce pyrolysis gas and pyrolysis char. During this process, the double-helix ribbon stirring paddle 109 and the heat storage medium flow pipe 108 with spiral fins on the outside stir simultaneously to achieve full mixing of the bed material and downward driving; The used pyrolysis catalyst and pyrolysis char enter the solid sieve 3 through the pyrolysis product outlet 107. The sieved pyrolysis char enters the carbon storage bin 4, and the sieved used pyrolysis catalyst enters the pyrolysis catalyst regeneration reactor 5 for regeneration. The pyrolysis gas is extracted by the first compression pump 117 and enters the hydrogenation reactor 6 through the pyrolysis gas discharge pipe 115; S3: Online hydrogenation of pyrolysis gas: The pyrolysis gas enters the hydrogenation reactor 6 from the pyrolysis gas discharge port 111 through the pyrolysis gas discharge pipe 115 and then from the hydrogenation reactant inlet 601. The catalyst enters the hydrogenation reactor 6 from the catalyst inlet 602. Hydrogen plasma is generated by the hydrogen plasma excitation device 604 to excite green hydrogen. In the hydrogenation reactor 6, the pyrolysis gas is subjected to online catalytic hydrodeoxygenation by the hydrogen plasma and the catalyst to generate hydrogenation products and produce used hydrogenation catalysts. The hydrogenation product outlet 608 is used to discharge the hydrogenation products; S4: Product condensation and separation: The hydrogenation products are discharged from the hydrogenation product outlet 608 and then enter the condenser 8 through the hydrogenation product inlet 801. The condenser 8 is used to condense the hydrogenation products to obtain condensed liquid products and non-condensable gas. The condensed liquid products are discharged through the condensed liquid product outlet 803, and the non-condensable gas is discharged through the non-condensable gas outlet 802.

[0064] In this embodiment, when cyclic hydrogenation is required, it further includes step S5: Product cyclic hydrogenation: The first part of the hydrogenation products discharged from the hydrogenation product outlet 608 enters the condenser 8 from the hydrogenation product inlet 801 through the first discharge pipe 613. The second part of the hydrogenation products is pumped back to the hydrogenation reactant inlet 601 by the compression pump 610 provided on the second discharge pipe 614 and enters the hydrogenation reactor 6 again to perform step S3.

[0065] In this embodiment, when a pyrolysis catalyst regeneration system is provided, it further includes step S6: pyrolysis catalyst cyclic regeneration. The used pyrolysis catalyst enters the pyrolysis catalyst regeneration reactor 5 through the used pyrolysis catalyst discharge pipeline 305. Air enters the pyrolysis catalyst regeneration reactor 5 from the first hot air inlet 502. The used pyrolysis catalyst particles and air undergo a combustion reaction, and the carbon deposits on the used catalyst are removed. After being separated by the cyclone separator in the pyrolysis catalyst regeneration reactor, the hot flue gas is discharged from the first hot flue gas outlet 503 at the upper end, and the regenerated pyrolysis catalyst is discharged from the regenerated pyrolysis catalyst outlet 504. After passing through the regenerated pyrolysis catalyst three-way valve 505 and the regenerated pyrolysis catalyst inflow pipeline 113, it enters the pyrolysis reactor 1 to perform step S2.

[0066] In this embodiment, when a hydrogenation catalyst regeneration system is provided, it further includes step S7: hydrogenation catalyst cyclic regeneration. The used hydrogenation catalyst enters the hydrogenation catalyst regeneration reactor 7 from the used hydrogenation catalyst inlet 701 through the used hydrogenation catalyst discharge pipeline 612. Air enters the hydrogenation catalyst regeneration reactor 7 from the second air inlet 702. The used hydrogenation catalyst particles and air undergo a combustion reaction, and the carbon deposits on the used catalyst are removed. After being separated by the cyclone separator in the hydrogenation catalyst regeneration reactor, the hot flue gas is discharged from the second hot flue gas outlet 703 at the upper end, and the regenerated hydrogenation catalyst is discharged from the regenerated hydrogenation catalyst outlet 704. After passing through the regenerated hydrogenation catalyst three-way valve 705 and the regenerated hydrogenation catalyst inflow pipeline 615, it enters the hydrogenation reactor 6 to perform step S3.

[0067] In summary, this embodiment also discloses a method for online upgrading of biomass pyrolysis driven by renewable energy. The catalytic pyrolysis of biomass is driven by solar thermal energy and renewable green electricity for heating, and a plasma torch 604 is driven by renewable green electricity to excite green hydrogen to generate high-energy active hydrogen plasma for online hydrogenation of biomass pyrolysis gas, enabling the low-carbon and high-value conversion of biomass under the drive of renewable energy.

[0068] The above are all the preferred embodiments of this application, and the protection scope of this application is not limited thereby. 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 biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy, characterized in that: Comprising: A solar heat collection system that uses sunlight to heat a heat storage medium; A catalytic pyrolysis system, including a pyrolysis reactor for catalytic pyrolysis of biomass to produce pyrolytic carbon and pyrolysis gas. The pyrolysis reactor is a downward moving bed structure, in which a double spiral ribbon agitator is rotatably provided; A plurality of heat storage medium flow pipes are also rotatably provided in the pyrolysis reactor, and spiral fins are provided on the outer periphery of the heat storage medium flow pipes; The heat storage medium heated by the solar heat collection system flows in the heat storage medium flow pipes to supply heat for the biomass pyrolysis reaction in the pyrolysis reactor; A plasma hydrogenation system, including a hydrogenation reactor for catalytic hydrodeoxygenation of the pyrolysis gas produced by the pyrolysis reactor through hydrogen plasma and a catalyst; A condensation system for condensing the hydrogenation products of the plasma hydrogenation system.

2. The biomass pyrolysis-gas phase hydrogen upgrading system driven by renewable energy according to claim 1, characterized in that: The double spiral ribbon agitator is arranged at the center of the pyrolysis reactor, and a plurality of the heat storage medium flow pipes are equally angularly and concentrically distributed in the pyrolysis reactor.

3. A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 2, characterized in that: The rotation direction of the agitator is opposite to that of the heat storage medium flow pipes.

4. A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 1, characterized in that: The solar heat collection system includes a condenser, a heat storage tower, and a buffer tank. The condenser is used to collect and reflect sunlight onto the heating chamber at the top of the heat storage tower. The heating chamber is used to receive the concentrated sunlight and heat the heat storage medium. The heating chamber is connected to the heat storage medium flow pipes, and the buffer tank is used for supplementing or removing the heat storage medium.

5. A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 1, characterized in that: The catalytic pyrolysis system further includes a screw feeder, a solid sieve, a carbon storage bin, and a pyrolysis catalyst regeneration reactor. The screw feeder is used to feed biomass raw materials into the pyrolysis reactor. The solid sieve is used to separate the mixture of waste catalyst and biochar discharged from the reactor. The carbon storage bin is used to store the sieved biochar. The pyrolysis catalyst regeneration reactor is used to regenerate the sieved waste pyrolysis catalyst.

6. The biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 1, characterized in that: The plasma hydrogenation system further includes a hydrogenation catalyst regeneration reactor for regenerating waste hydrogenation catalysts.

7. A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 1, characterized in that: The hydrogenation products produced by the hydrogenation reactor are divided into a first part and a second part. The first part enters the condensation system, and the second part enters the hydrogenation reactor for cyclic hydrogenation.

8. A biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to claim 1, characterized in that: It further includes a pyrolysis catalyst regeneration system. The pyrolysis catalyst regeneration system includes a pyrolysis catalyst regeneration reactor for removing carbon deposits on the waste pyrolysis catalyst to generate a regenerated pyrolysis catalyst and re-inputting the regenerated pyrolysis catalyst into the pyrolysis reactor.

9. A biomass pyrolysis-gas phase hydrogenation upgrading method driven by renewable energy, which uses a biomass pyrolysis-gas phase hydrogenation upgrading system driven by renewable energy according to any one of claims 1-8, characterized in that: Including the following steps: Solar concentrating heat collection: Using sunlight to heat the heat storage medium and introducing the heated heat storage medium into the heat storage medium pipeline; Biomass catalytic pyrolysis: Inputting dry biomass raw materials, catalysts, and carrier gas into the pyrolysis reactor, and realizing biomass catalytic pyrolysis through the cooperation of three heating methods: electric heating, heat storage medium pipeline heating, and regenerated pyrolysis catalyst heating, so that the biomass pyrolyzes to produce pyrolysis gas and pyrolytic carbon; Online hydrogenation of pyrolysis gas: Introducing pyrolysis gas into the hydrogenation reactor and adding a catalyst, introducing hydrogen into a plasma excitation device to generate hydrogen plasma, and performing catalytic hydrodeoxygenation of the pyrolysis gas through hydrogen plasma and the catalyst to generate hydrogenation products; Product condensation and separation: The hydrogenated product enters the condensation system, and after condensation, a condensed liquid product and a non-condensable gas are obtained respectively.

10. A method for pyrolysis-gas phase hydrogenation upgrading of biomass driven by renewable energy according to claim 9, characterized in that: In the biomass catalytic pyrolysis step, the double-helical ribbon stirring paddle and the heat storage medium flow pipe with spiral fins on the outside are stirred simultaneously to achieve full mixing of the bed material and downward driving.

Images