The present disclosure belongs to the field of greenhouse gas utilization and renewable energy utilization or consumption, and relates to system and method for utilizing renewable electricity by methanol synthesis via plasma-catalysis CO2 hydrogenation.
The catalytic hydrogenation of CO2 for methanol synthesis is a prominent research focus internationally. CO2 is the major greenhouse gas with a wide range of sources, while green hydrogen can be readily obtained through water electrolysis by renewable energy. Methanol, a high value-added product, is liquid with the potential to directly utilize existing transportation and power infrastructure. It boasts high energy density, clean and efficient combustion, making it an ideal green fuel or hydrogen carrier. Additionally, methanol is the fourth largest basic chemical feedstock, capable of being converted into hundreds of chemical products. With the rise of renewable energy and the significant reduction in investment and operating costs, CO2 hydrogenation for methanol synthesis driven by renewable energy has attracted significant attention.
Research and development into methanol synthesis from CO2 hydrogenation under thermocatalytic conditions began early. In 1993, Lurgi launched the world's first demonstration project for CO2 hydrogenation to methanol. In China, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Shanghai Institute of Advanced Research and others have conducted extensive industrial research. For instance, a skid-mounted device developed by the Dalian Institute of Chemical Physics and PetroChina has achieved a CO2 conversion rate of 20% and methanol selectivity of 70%.
However, thermocatalytic CO2 hydrogenation for methanol synthesis faces several challenges: Thermodynamic and kinetic limitations results in a low single-pass conversion rate (generally <20%) and require operation under high pressure conditions (generally >5 Mpa). Additionally, the catalytic process is complex with low flexibility, long response times (typically on the order of hours), and difficulty adapting to the significant variability of renewable electricity, limiting its scalability and broader application.
Therefore, there is a need for a method and system that can overcome these challenges, enabling low-energy, flexible, and controlled conversion of CO2 to methanol, while accommodating the fluctuations of renewable electricity. Such advancement would greatly enhance the application prospects of renewable energy-driven CO2 hydrogenation, enabling efficient chemical energy storage, greater utilization of renewable energy and the collaborative conversion of greenhouse gas CO2. This would offer a transformative pathway to achieving carbon peak and carbon neutrality goals.
The present disclosure aims to provide a system and method for utilizing renewable electricity by methanol synthesis via plasma-catalysis CO2 hydrogenation, addressing the shortcomings of prior art.
In a first aspect, a system for utilizing renewable electricity by methanol synthesis via plasma-catalysis CO2 hydrogenation is provided, including a plasma jet reaction tower, a methanol synthesis reactor, a feed system, a storage and pressurization system, a power source and a purification treatment system.
The feed system is configured to provide H2 and CO2 for a plasma jet reactor.
The plasma jet reaction tower is configured to pre-activate and convert CO2 by using plasma jet, causing CO2 and H2 to undergo reverse water-gas shift reaction, producing a CO/CO2/H2 mixed intermediate product at atmospheric pressure and low temperature.
The storage and pressurization system, comprising a mixed gas intermediate storage tank and a multi-stage pressurization system, is configured to store and pressurize the CO/CO2/H2 mixed gas produced by the plasma jet reactor.
The methanol synthesis reactor is configured to catalytically synthesize methanol from the CO/CO2/H2 mixed gas conveyed by the storage and pressurization system.
The power source is configured to supply renewable electricity to the plasma jet reactor, the methanol synthesis reactor, and the remaining system.
The purification treatment system is configured to separate methanol from the remaining reaction gas and purify the methanol product.
Further, the feed system includes a water electrolysis hydrogen production reactor, a H2 storage tank, a CO2 storage tank, a water pump, a first flow controller and a heat exchanger. The water pump, the first flow controller and the heat exchanger are configured to convey H2O to the water electrolysis hydrogen production reactor and control flow, and the water electrolysis hydrogen production reactor is connected to the H2 storage tank.
Further, each output of the H2 storage tank, the CO2 storage tank and the mixed gas intermediate storage tank is equipped with a check valve, a flow controller and a centrifugal pump.
Further, the top of the plasma jet reaction tower is provided with a gas collecting unit that directs gas to the mixed gas intermediate storage tank, while the bottom has a liquid collecting pipeline. Three vertically staggered plasma jet reaction groups are mounted on one side of the tower body, with each group consisting of six symmetrically arranged plasma jet reactors in a hexagonal array, fixed to a disk-shaped base. On the opposite side of the tower, three sight glasses allow observation of the reaction process, and temperature and pressure sensors are installed on the tower's surface.
Further, each plasma jet reactor includes an outer electrode, an inner electrode, a CO2/H2 inlet and a base.
The outer electrode, fixed to an insulating base, is a hollow sleeve electrode with a tapered outlet at an upper portion.
The inner electrode, conical in shape, is positioned at the lower-mid part of the hollow structure of the outer electrode, and integrally formed by a lower cylinder and an upper cone frustum. The inner electrode is fixed to the base and connected to a high voltage plasma power source via an electrode lead penetrating through the base; an outer wall of the inner electrode is parallel to an inner wall of the outer electrode; the H2/CO2 inlet is formed in a wall surface of the outer electrode, a H2/CO2 stream inlet is provided at a bottom of the plasma jet reactor and tangentially introduced from the bottom to form a swirling rising flow in a gap between the inner electrode and the outer electrode, to drive an arc between the inner electrode and outer electrodes to rise rotationally, and plasma is ejected in a jet form under the action of the tapered outlet. The outer and inner electrodes are connected to a frequency-adjustable high voltage alternating current (AC) power source.
Further, the methanol synthesis reactor is provided with a CO/CO2 hydrogenation methanol synthesis reaction unit and a crude methanol outlet. CO/CO2 and H2 are selectively converted into crude methanol over copper-based composite nanocatalyst, which is then purified through the purification system. This enables efficient chemical energy storage of surplus/valley electricity and the collaborative conversion of greenhouse gas CO2.
Further, the multi-stage pressurization system includes a booster pump, a buffer tank, a back pressure valve and a real-time pressure monitoring system.
Further, the purification treatment system includes: a reheater, a gas-liquid desuperheater, a flash tank, a methanol rectification tower and a methanol storage tank connected to one another in sequence. A liquid channel of the flash tank directly connects to the rectification tower, while the gas channel of the flash tank is connected to the methanol synthesis reactor and the methanol rectification tower. The purification treatment system is configured to separate the methanol from the remaining reaction gas and purify the methanol.
Further, the power source includes a water electrolysis hydrogen production power source, a plasma jet reactor power source and a multi-stage pressurization system power source, which are configured to supply power to the water electrolysis hydrogen production reactor, the plasma jet reactor and the multi-stage pressurization system respectively, all powered by off-grid renewable energy.
In a second aspect, a method for utilizing renewable electricity by methanol synthesis via plasma-catalysis CO2 hydrogenation is provided, including:
Step 1, activating the power source for water electrolysis to produce hydrogen, and directly introducing the produced hydrogen into the H2 storage tank for storage.
Step 2, opening the CO2 storage and H2 storage tank, mixing the gases in a specific ratio and introducing them into the plasma jet reactor, forming a swirling flow inside the reactor; activating the power source to form an arc between the inner and outer electrodes which then rises rotationally, ejecting plasma jet under the action of a tapered outlet. The reactor's power and gas flow are adjusted for optimal performance, while real-time temperature monitoring is conducted. CO2 undergoes pre-activation and the following reaction occurs:
CO2+H2═CO+H2O.
Step 3, the mixed gas produced by the reaction is over rising after passing an air distributor, introducing the mixed gas into a mixed gas intermediate storage tank for storage, and water flows out from a lower liquid collecting pipeline.
Step 4, the mixed gas is pressurized to 3-5 MPa using the multi-stage pressurization system and introduced into the methanol synthesis reactor, where it undergoes catalytic conversion into methanol.
Step 5, sequentially cooling, by a heat exchanger and a gas-liquid desuperheater, a gas-liquid mixture of the methanol produced after reaction in the methanol synthesis reactor and unreacted gas, performing gas-liquid separation on the cooled gas-liquid mixture using a flash tank, purifying, by a methanol rectification tower, separated liquid methanol, sending the purified liquid methanol to a methanol storage tank, passing separated gas through a separator, collecting and uniformly treating a part of the separated gas, and returning another part of the separated gas to the methanol synthesis reactor for further reaction.
Compared with the prior art, the present disclosure has the following advantages:
(1) Methanol is synthesized using a two-stage CO2 hydrogenation process, overcoming the thermodynamic bottlenecks of direct CO2 hydrogenation. Plasma efficiently pre-activates and partially converts CO2 at atmospheric pressure, producing CO/CO2/H2 that can be more efficiently synthesized into methanol in both kinetic and thermodynamic terms, thereby remarkably improving the overall performance.
(2) CO2 is activated by the plasma jet at atmospheric pressure through high-energy electrons and excited-state reactive species, facilitating the reverse water-gas shift reaction with H2. No catalyst is needed during the reaction process, addressing issues of catalyst deactivation and high reaction temperatures in traditional thermocatalytic reverse water-gas shift reaction.
(3) The fractions of CO/CO2/H2 in the outlet mixed gas can be flexibly adjusted by regulating the power, the gas flow rate and other parameters of the plasma jet reactors, thereby optimizing the selectivity and the conversion rate of the catalytic methanol synthesis stage.
(4) A storage system decouples the plasma reactors from the methanol synthesis reactor, mitigating the impact of fluctuations in plasma reactions on methanol synthesis reaction.
(5) The entire system is powered by renewable energy. Plasma's rapid start/stop capability and fast reaction rates make it well-suited to the intermittency of renewable power sources, offering strong application potential in regions with abundant wind and solar energy, such as Inner Mongolia, China.
The detailed description of the present disclosure is further described in detail below in combination with the accompanying drawings.
As shown in
The reactors include a water electrolysis hydrogen production reactor 5, a plasma jet reactor 15 and a methanol synthesis reactor 27, and all the reactors are equipped with temperature monitoring devices.
The water electrolysis hydrogen production reactor 5 is a solid oxide electrolytic cell (SOEC) reaction chamber, with a working temperature of 600° C. to 1000° C., and a main structure includes a cathode, an anode and an electrolyte layer. The cathode uses Ni/YSZ porous metal ceramic, the anode is a rare-earth-element containing perovskite (ABO3) oxide, and the electrolyte layer is an oxygen ion conductor (YSZ or ScSZ, etc.).
In the water electrolysis hydrogen production reactor 5, H2 is introduced through a hydrogen outlet pipe into a storage tank to be stored, the storage tank is connected with a first check valve 7, a second flow controller 8 and a first centrifugal pump 9 in sequence, and oxygen is discharged by an oxygen outlet pipe.
As shown in
The outer electrode and the inner electrode are connected to a frequency-adjustable high voltage alternating current power source with frequency of 5 to 40 kHz, a maximum output voltage of 20 kV and maximum power of 1 kW.
The outer electrode, fixed to an insulating base, is a hollow sleeve electrode with a tapered outlet at an upper portion.
The inner electrode, conical in shape, is positioned at the lower-mid part of the hollow structure of the outer electrode, and integrally formed by a lower cylinder and an upper cone frustum. The inner electrode is fixed to the base and connected to a high voltage plasma power source via an electrode lead penetrating through the base; an outer wall of the inner electrode is parallel to an inner wall of the outer electrode.
The H2/CO2 inlet is located at the bottom of the plasma jet reactor, and is tangentially introduced from the bottom to form a swirling rising flow in a gap between the inner and outer electrodes, so as to drive an arc between the inner and outer electrodes to rise rotationally, and plasma is ejected in a jet form under the action of a tapered outlet.
Further, the plasma jet reactors 15 are distributed and fixed on a disk-shaped base 18 in a symmetric array to form a reaction group, three reaction groups are evenly distributed on the same side of the plasma jet reaction tower 20 in a vertical staggered mode, three sight glasses 16 are correspondingly distributed on the other side and configured to observe a reaction process, a gas collecting unit is located at the top of the reaction tower, and liquid flows out from a bottom liquid collecting pipeline 14. Temperature and pressure sensors 17 are mounted on a wall surface of the reaction tower to monitor a state of the reaction system in real time.
The feed system is connected with a flow control device, and the feed system includes a vapor feed system and a CO2 feed system.
Further, a water pump is configured to supply water to a vapor producing device, and produced vapor enters the water electrolysis hydrogen production reactor through a vapor inlet valve and a vapor inlet pipe. The vapor feed system includes the water pump 1, the vapor producing device (heat exchanger 3) and a first flow controller 2. The water pump is connected with the heat exchanger through the first flow controller and supplies water, the heat exchanger achieves heat exchange between a product methanol and a reactant water, water is heated while methanol is cooled, and the produced vapor enters the water electrolysis hydrogen production reactor 5 through the vapor inlet valve and the vapor inlet pipe.
The CO2 feed system is configured to feed a reactant CO2, after being mixed with H2, the CO2 is introduced into the plasma jet reactor 15 from a gas inlet 19 to feed CO2. In the present embodiment, the CO2 feed system includes a CO2 storage tank 10, a second check valve 11, a third flow controller 12 and a second centrifugal pump 13.
The CO2 storage tank is configured to store CO2, and the second check valve, the third flow controller and the second centrifugal pump are connected with one another to be used for controlling the flow of CO2.
The power source includes a water electrolysis hydrogen production power source 4, a plasma jet reactor power source and a multi-stage pressurization system power source, all powered by off-grid renewable energy (such as photovoltaic power and wind power).
The water electrolysis hydrogen production power source is configured to supply renewable electricity to drive the electrochemical hydrogen evolution reaction in the water electrolysis hydrogen production reactor 5, finally completing the production of methanol under atmospheric pressure with the plasma jet reactor as the core. The water electrolysis hydrogen production power source is a direct current device. One end of a negative electrode line is connected with a hydrogen evolution pole of the water electrolysis hydrogen production reactor, and the other end is connected with a negative electrode of the direct current power source; and one end of a positive electrode line is connected with an oxygen evolution pole of the water electrolysis hydrogen production reactor, and the other end is connected with a positive electrode of the direct current power source.
The multi-stage pressurization system power source is configured to supply power to a booster pump, an electromagnetic valve and the like in a multi-stage pressurization system 25.
The storage and pressurization system is configured to store and pressurize the CO/CO2/H2 mixed gas produced by the plasma jet reactor. The storage and pressurization system includes a mixed gas intermediate storage tank 21, a third check valve 22, a fourth flow controller 23, a third centrifugal pump 24 and the multi-stage pressurization system 25.
A pressurization flow chart of the multi-stage pressurization system is as shown in
The purification treatment system is configured to separate methanol from the remaining reaction gas and purify the methanol product. A gas-liquid mixture produced after reaction in the methanol synthesis reactor is cooled through the heat exchanger 3 and a gas-liquid desuperheater 28 in sequence, gas-liquid separation is performed on the cooled gas-liquid mixture in a flash tank 29, separated liquid methanol is purified through a methanol rectification tower 31 and then stored in a methanol storage tank 32, gas separated by the flash tank and gas separated by the rectification tower pass through a separator 30, then part of the gas is collected and then treated uniformly, and the other part of the gas is returned to the methanol synthesis reactor 27 for further reaction.
In the present disclosure, two key reactions-plasma CO2 pre-activation/conversion and catalytic methanol synthesis-occur in two independent and isolated reaction chambers. Unlike traditional methanol synthesis methods, which rely on the direct thermocatalytic conversion of CO2, this method, utilizing plasma-catalysis CO2 hydrogenation, allows for these reactions to occur in separate reactors under different conditions. This separation enables the optimization of each step independently to achieve the best overall performance of the system. The inclusion of an intermediate storage system decouples the methanol synthesis reactor from the plasma jet reactor, ensuring that the methanol synthesis process remains unaffected by fluctuations in the plasma jet reactor. Meanwhile, CO2 is partially converted to CO by adopting plasma technology. This process eliminates the need for a catalyst, thereby addressing issues of catalyst deactivation and high reaction temperatures associated with traditional thermocatalytic reverse water-gas shift reactions. Furthermore, the system allows for the adjustment of product component ratios by regulating gas flow, power, and other parameters, enabling more efficient catalytic synthesis of methanol from the CO/CO2/H2 mixed gas, which significantly enhances the overall process efficiency.
An embodiment of the present disclosure provides a method for utilizing renewable electricity by methanol synthesis via plasma-catalysis CO2 hydrogenation, and the method includes the following steps:
1, The power source 4 is activated to perform water electrolysis hydrogen production, and produced hydrogen is directly introduced into the H2 storage tank 6 for storage.
2, The CO2 storage tank 10 and the H2 storage tank 6 are opened, the gases are mixed in a specific ratio of 1:3 and introduced them into the plasma jet reactor 15, a swirling flow is formed inside the reactor, the power source is activated to form an arc between the inner and outer electrodes which then rises rotationally, plasma jet is ejected under the action of a tapered outlet. The reactor's power and gas flow are adjusted for optimal performance, within a range of 50 to 300 W and a range of 1 to 10 L/min, respectively, while real-time temperature monitoring is conducted. CO2 undergoes pre-activation and the following reaction occurs:
CO2+H2═CO+H2O.
3, The mixed gas produced after the reaction rises after passing an air distributor, and is introduced into a mixed gas intermediate storage tank 21 to be stored. Water flows out from a lower liquid collecting pipeline.
4, After being pressurized to 3-5 MPa through a multi-stage pressurization system, gas in the mixed gas intermediate storage tank 21 is introduced into the methanol synthesis reactor 27 to synthesize methanol over a catalyst. The specific pressurization data are as follows:
5, A gas-liquid mixture of the methanol produced after reaction in the methanol synthesis reactor 27 and unreacted gas is cooled through a heat exchanger 3 and a gas-liquid desuperheater 28 in sequence, gas-liquid separation is performed on the cooled gas-liquid mixture by using a flash tank 29, separated liquid methanol is purified through a methanol rectification tower 31 and then sent to a methanol storage tank 32, a pressure in the methanol rectification tower 31 is controlled to be 0.15 MPa, separated gas passes through a separator 30, then part of the gas is collected and then treated uniformly, and the other part of the gas is returned to the methanol synthesis reactor 27 for further reaction.
The above description is only a preferred implementation of the present disclosure, and although the present disclosure has been disclosed as above through preferred embodiments, it is not intended to limit the present disclosure. Any person skilled in the art may use the method and technical content disclosed above to make many possible changes and modifications to the technical solution of the present disclosure, or modify it into equivalent embodiments with equivalent changes, without departing from the scope of the technical solution of the present disclosure. Therefore, any simple amendments, equivalent changes, and modifications made to the above embodiments in accordance with the technical essence of the present disclosure that do not depart from the content of the technical solution of the present disclosure still fall within the scope of protection of the technical solution of the present disclosure.
Number | Date | Country | Kind |
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202311418656.0 | Oct 2023 | CN | national |
This application is a continuation of International Application No. PCT/CN2024/075384, filed on Feb. 2, 2024, which claims priority to Chinese Application No. 202311418656.0, filed on Oct. 30, 2023, the contents of both of which are incorporated herein by reference in their entireties.
Number | Date | Country | |
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Parent | PCT/CN2024/075384 | Feb 2024 | WO |
Child | 18895290 | US |