CN111302302A - Thermochemical hydrogen production system based on microwave heating and hydrogen production method and application thereof - Google Patents
Thermochemical hydrogen production system based on microwave heating and hydrogen production method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermochemical hydrogen production, and particularly relates to a thermochemical hydrogen production system based on microwave heating and a hydrogen production method and application thereof. The hydrogen production device has the following structure: the inlet of the preheater is communicated with the carrier gas storage device, and a flow controller is arranged between the inlet of the preheater and the carrier gas storage device; the outlet of the preheater is respectively communicated with the inlet of the steam generator and one end of the second three-way valve through the first three-way valve; the other two ports of the second three-way valve are respectively communicated with the outlet of the superheater and the inlet of the reactor; the reactor is arranged in the microwave generating device; the outlet of the steam generator is communicated with the inlet of the superheater through a pipeline; the outlet of the reactor, the condenser, the drying device and the collecting device are communicated in sequence; the chromatograph is arranged on a communication pipeline between the drying device and the collecting device. The heating time of the metal oxide is short, the power consumption is low, the experiment cost is low, the repeated experiment period is shortened, and the effective energy utilization rate is greatly improved.
Description
Technical Field
The invention belongs to the technical field of thermochemical hydrogen production, and particularly relates to a thermochemical hydrogen production system based on microwave heating and a hydrogen production method and application thereof.
Background
This information disclosed in this background of the invention is only for the purpose of increasing an understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Since the 21 st century, countries around the world have given high attention to carbon dioxide emissions and global warming issues. People develop and utilize energy and gradually convert the energy into gas fuels such as natural gas, hydrogen and the like, and the hydrogen energy is used as an optimal renewable energy carrier, so that the hydrogen energy has the advantages of rich resources, renewability, environmental protection, high efficiency and the like. The existing hydrogen production technology is various and comprises chemical, biological, electrolytic and photolytic treatment processes. The main global liquid hydrogen production mode is natural gas steam reforming hydrogen production. In the beginning of the 21 st century, Kodama and Steinfeld proposed a new hydrogen production process, a chemical looping steam reforming hydrogen production and syngas technology. The technology couples the advantages of the technology of preparing the synthetic gas by partially oxidizing the lattice oxygen and the technology of preparing the hydrogen by decomposing water, the purity of the obtained hydrogen is high, and the synthetic gas (H) is2a/CO ═ 2) ratio is suitable. For example, patent document CN110407171A discloses a thermochemical hydrogen production reaction performance evaluation system and method based on a solar concentrating simulator, which is characterized in that gaseous methane, ethane, oxygen and their mixture, or liquid methanol, ethanol, water and their mixture are used as raw materials, the solar concentrating simulator is used to provide a temperature of 200 ℃ to 1000 ℃ to react in a catalyst-filled microchannel reactor to generate hydrogen, carbon monoxide and carbon dioxide, the product is purged by inert gas and cooled by a condenser, and after the reaction is finished, the product is collected and analyzed and detected.
Currently, hydrogen production by water splitting, and in particular two-step thermochemical water splitting, is given extensive consideration. Thermochemical water splitting refers to a process that combines chemical reactions to cause water to be split at temperatures lower than direct thermal splitting. Specifically, in the thermochemical water splitting reaction, oxides in different oxidation states undergo redox reactions to split water into hydrogen and oxygen, for example, a metal oxide in a high oxidation state is pyrolyzed at a high temperature into a metal oxide in a low oxidation state and oxygen (thermal reduction reaction, temperature is around 1500 ℃), and the metal oxide in a low oxidation state reacts with water to generate hydrogen and is oxidized into a metal oxide in a high oxidation state (hydrolysis reaction, temperature is around 800 ℃). In such thermochemical water splitting processes, it is important to reduce the temperature required for the reaction, in particular to reduce the temperature required for the pyrolysis of the metal oxide in a high oxidation state. The catalyst is crucial in the thermochemical hydrogen production reaction, and the effective catalyst can greatly reduce the reaction temperature of the thermochemical reaction and improve the reaction efficiency. It has been demonstrated that doped ceria and nickel ferrite metal oxides can be effectively used for thermochemical water splitting.
However, the inventors believe that: in the process of evaluating the hydrogen production performance of the catalyst, the economic cost of utilizing the solar light collecting simulator as a heat source is too high, the temperature required by high-temperature pyrolysis of the metal oxide is often as high as about 1500 ℃, the process of pyrolyzing the metal oxide is as long as 30-60min, the lengthy heating time leads to an experimental period of about 1.5-2h, and the catalyst is easy to be sintered and inactivated under the high temperature for a long time, so that a plurality of problems exist in the aspects of the experimental period, the experimental cost, the energy efficiency and the like.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a thermochemical hydrogen production system and a thermochemical hydrogen production method based on microwave heating, and provides preparation and application of a wave-absorbing material.
The invention provides a thermochemical hydrogen production system based on microwave heating.
The invention provides a thermochemical hydrogen production method based on microwave heating.
The invention also provides a thermochemical hydrogen production system based on microwave heating and application of the hydrogen production method thereof.
In order to realize the purpose, the invention discloses the following technical scheme:
firstly, the invention discloses a thermochemical hydrogen production system based on microwave heating, which comprises: carrier gas storage device, pre-heater, microwave generating device, reactor, condenser, drying device, chromatograph, collection device, steam generator and over heater. Wherein: the inlet of the preheater is communicated with the carrier gas storage device, and a flow controller is arranged between the inlet of the preheater and the carrier gas storage device. The outlet of the preheater is respectively communicated with the inlet of the steam generator and one end of a second three-way valve through a first three-way valve, the other two ports of the second three-way valve are respectively communicated with the outlet of the superheater and the inlet of the reactor, and the reactor is arranged in the microwave generating device. The outlet of the steam generator is communicated with the inlet of the superheater through a pipeline, the outlet of the reactor, the condenser, the drying device and the collecting device are sequentially communicated, and the chromatograph is arranged on a communication pipeline between the drying device and the collecting device.
As a further technical solution, the carrier gas in the carrier gas storage device is an inert gas, such as Ar gas. In addition, nitrogen may be used as the carrier gas.
As a further technical scheme, the material of the reactor is high-temperature-resistant quartz.
As a further technical scheme, microwave radiation is input into the reaction cavity through the microwave generated by the microwave generating device through the waveguide, the reactor is placed in the reaction cavity, and the catalyst is placed in the reactor.
As a further technical scheme, the preheater and the superheater are both electrically heated, the preheater is mainly used for preheating the carrier gas from the carrier gas storage device, so as to reduce the temperature reduction caused by gas-liquid mixing and ensure that the carrier gas can carry a certain amount of water vapor, and the superheater is mainly used for heating the water vapor to the superheating temperature and ensuring that the hydrolysis reaction can reach the reaction temperature (usually 800 ℃).
As a further technical scheme, the steam generator is a device for heating water through a water bath or an oil bath, and water vapor generated by the steam generator is carried into the superheater through a carrier gas.
As a further technical scheme, the drying device adopts a water removal device, and the main function of the water removal device is to remove water in the product.
As a further technical scheme, the water removal device is a container filled with allochroic silica gel, and the gaseous product enters the water removal device to be dehydrated under the pushing of the carrier gas.
As a further technical scheme, the connecting pipelines of the reactor inlet and the superheater outlet are provided with heat insulation materials.
As a further technical scheme, the condenser is of a jacket type structure and can realize condensate circulation through a pumping device. The condenser also includes a trap for storing liquid water condensed from the gaseous products.
As a further technical solution, the chromatograph is used for detecting the generated mixed gas component.
As a further technical scheme, the device also comprises an electric resistance furnace which is used for heating the reactor in the hydrolysis reaction to enable the catalyst in the reactor to react with water to generate hydrogen and oxidize the hydrogen into metal oxide with high oxidation state. The invention can effectively explore the hydrogen production performance of the catalyst by combining the microwave generating device and the traditional heating equipment.
Further, when hydrogen is produced by adopting the wave-absorbing catalyst, the wave-absorbing catalyst is heated by a microwave generating device under the protective atmosphere, so that the conversion from the high oxidation state metal oxide loaded on the wave-absorbing catalyst to the low oxidation state metal oxide is realized, the low oxidation state metal oxide can further undergo hydrolysis reaction with water vapor under the heating condition to be oxidized into the high oxidation state metal oxide and generate hydrogen, and the step of converting the high oxidation state metal oxide to the low oxidation state metal oxide is repeated.
Further, heating the wave absorption catalyst by a microwave generating device under a protective atmosphere, wherein when the loaded high oxidation state metal oxide is converted into the low oxidation state metal oxide, the heating power is 500-900W, and the heating time is 3-5 min. This time is significantly reduced relative to the 0.5-1h time required for a solar simulator or conventional heating tool, thereby reducing cycle time and also reducing experimental costs.
Furthermore, a microwave generating device is adopted to heat the low oxidation state metal oxide under the protective atmosphere, so that the heating power is 500-900W when the low oxidation state metal oxide is subjected to hydrolysis reaction by water vapor.
Furthermore, when the microwave generator is used for thermochemical water splitting to produce hydrogen, the oxidation and reduction reactions are carried out under the power conditions of microwaves and the like, so that the hydrogen can be continuously regenerated.
Furthermore, when the microwave generator is used for thermochemical water splitting to produce hydrogen, oxidation and reduction reactions are carried out under the microwave variable power condition, namely, the oxidation reaction is carried out at high power, and the hydrolysis reaction is carried out at low power, so that the continuous regeneration of the hydrogen can be realized.
As a further technical scheme, the catalyst is a metal oxide loaded on a porous wave-absorbing matrix, or a metal oxide doped with a strong wave-absorbing substance, or a metal oxide pressed into a porous structure. The metal oxide includes but is not limited to iron-based oxide, cerium-based oxide and perovskite-type oxide, and the wave-absorbing matrix includes but is not limited to porous silicon carbide ceramic foam.
Secondly, the invention discloses a thermochemical hydrogen production method based on microwave heating, which comprises the following specific steps:
(1) putting a catalyst into a reactor, placing the reactor into a reaction cavity of a microwave generating device, ensuring the sealing property of a communicating pipeline, opening all valves of a three-way valve, opening carrier gas and setting the flow of the carrier gas to purge each part of the system;
(2) adjusting the state of the three-way valve, only forming a carrier gas storage device → a flow controller → a preheater → a reactor passage, and opening the preheater/steam generator/superheater until the preheater/steam generator/superheater reaches a preset temperature;
(3) setting the heating power and the heating time of a microwave generating device, and operating the microwave generating device to perform thermal reduction reaction after the preheater/steam generator/superheater reaches a preset temperature;
(4) after the thermal reduction reaction is finished, adjusting the state of a three-way valve to form a carrier gas storage device → a flow controller → a preheater-steam generator-superheater-reactor passage, setting microwave heating power and heating time, and operating a microwave generating device to perform hydrolysis reaction;
(5) the cooled and dried gaseous product was analyzed by detection in a chromatograph.
Furthermore, the invention discloses a thermochemical hydrogen production method based on microwave combined conventional heating equipment, which comprises the following specific steps:
(1) putting a catalyst into a reactor, placing the reactor into a reaction cavity of a microwave generating device, ensuring the sealing property of a communicating pipeline, opening all valves of a three-way valve, opening carrier gas and setting the flow of the carrier gas to purge each part of the system;
(2) adjusting the state of the three-way valve, only forming a carrier gas storage device → a flow controller → a preheater → a reactor passage, and opening the preheater/superheater until the preheater/superheater reaches a preset temperature;
(3) setting the heating power and the heating time of a microwave generating device, and operating the microwave generating device to perform thermal reduction reaction after the preheater/superheater reaches a preset temperature;
(4) after the thermal reduction reaction is finished, transferring the reactor and the connecting pipeline thereof to a resistance furnace, opening the steam generator/resistance furnace, and waiting for the steam generator/resistance furnace to reach a preset temperature;
(5) when the steam generator/resistance furnace reaches a preset temperature, adjusting the state of the three-way valve to form a carrier gas storage device → a flow controller → a preheater-steam generator-superheater-reactor channel for hydrolysis reaction;
(6) the cooled and dried gaseous product was analyzed by detection in a chromatograph.
Finally, the invention discloses application of the thermochemical hydrogen production system based on microwave heating in the field of energy.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention pyrolyzes metal oxide by microwave, and has the characteristics of low energy consumption and rapid temperature rise: when a solar simulator or a traditional heating tool is used for carrying out the reduction step, the reduction step usually needs to be heated for 0.5-1h to obtain a relatively obvious thermal reduction rate, and when microwaves act on a substance with a strong wave absorption characteristic, electromagnetic waves can be dissipated in a relatively short time to rapidly increase the temperature, so that the thermal reduction step only needs 3-5 min. Therefore, the hydrogen production device related by the invention can effectively solve the problem of long heat treatment time in the thermochemical cycle hydrogen production process by utilizing the hot spot effect of microwave heating.
(2) Compared with the traditional heating equipment and a solar simulator, the microwave heating device has the advantages that the cycle period is greatly shortened, the radiant heat loss and the heat dissipation loss are reduced, a large amount of hydrogen is generated, and the energy utilization rate is improved.
(3) Aiming at the influence of the discharge phenomenon on the performance evaluation of the catalyst, the invention can simulate solar heating to explore the hydrogen production performance of the catalyst by the combined use of the microwave generating device and the traditional heating equipment, namely, the traditional heating equipment is used for heating the reactor for hydrolysis reaction, thereby not only shortening the cycle period, but also reducing the experiment cost.
(4) Compared with the complexity and difficulty of the solar simulator in the aspects of experiment cost, equipment adjustment and temperature control, the invention has the advantages that the microwave generating device is simple, convenient and efficient as a heat source, and industrial microwave equipment and common household microwave ovens can be used for experiment exploration.
(5) Generally, a directly prepared powdery metal oxide capable of being used for thermochemical hydrogen production is a weak wave-absorbing material, is difficult to heat to a temperature for realizing a thermal reduction reaction in a microwave field, has poor cycle stability, and is easily carried away. According to the invention, the metal oxide is loaded on the strong wave absorbing material or is directly pressed into a porous structure after being doped with the strong wave absorbing material, so that the requirements of thermal reduction reaction can be met, and the high-temperature resistant characteristic and the cycling stability are better.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic structural diagram of a thermochemical hydrogen production system based on microwave heating according to a first embodiment of the present invention.
FIG. 2 is a microscopic view of a porous silicon carbide ceramic foam (left panel) and a silicon carbide ceramic foam loaded with a high oxidation state metal oxide (right panel) according to a second embodiment of the present invention.
FIG. 3 is a graph showing the hydrogen yield from thermochemical hydrogen production under 900W microwave power in a second embodiment of the invention (left graph) and the hydrogen yield from 5 cycles (right graph).
FIG. 4 is a graph showing the variation of hydrogen and oxygen concentrations in thermochemical hydrogen production under 700W microwave power and the hydrogen yields obtained from 5 cycles in the third example of the invention.
FIG. 5 shows the variation of hydrogen and oxygen concentrations and the hydrogen yields obtained from 5 cycles of thermochemical hydrogen production under 500W of microwave power in a fourth embodiment of the invention.
FIG. 6 is an electron micrograph of fresh catalyst and catalyst after 3 cycles at 700W microwave power in a fifth example of the present invention.
The designations in the above figures represent respectively: 1-carrier gas storage device, 2-flow controller, 3-preheater, 4-first three-way valve, 5-second three-way valve, 6-microwave generation device, 7-reactor, 9-condenser, 10-drying device, 11-chromatograph, 12-collection device, 13-steam generator, 14-superheater, 15-resistance furnace and 16-trap.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
For convenience of description, the words "up", "down", "left" and "right" in the present invention, if any, merely indicate that the directions of movement are consistent with those of the drawings, and do not limit the structure, but merely facilitate the description of the invention and simplify the description, rather than indicate or imply that the referenced device or element needs to have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention.
Term interpretation section: the terms "mounted," "connected," "fixed," and the like in the present invention are to be understood in a broad sense, and for example, the terms "mounted," "connected," and "fixed" may be fixed, detachable, or integrated; the two components can be connected mechanically or electrically, directly or indirectly through an intermediate medium, or connected internally or in an interaction relationship, and the terms used in the present invention should be understood as having specific meanings to those skilled in the art.
As described in the background art, the existing hydrogen production by using a solar light-gathering simulator as a heat source has the problems of experiment period, experiment cost, energy efficiency and the like. Therefore, the invention provides a thermochemical hydrogen production system based on microwave heating, a wave-absorbing catalyst, a preparation method and a use method thereof; the invention will now be further described with reference to the accompanying drawings and detailed description.
First embodimentReferring to fig. 1, a thermochemical hydrogen production apparatus based on microwave heating according to the present invention includes a carrier gas storage device 1, a flow controller 2, a preheater 3, a first three-way valve 4, a second three-way valve 5, a microwave generation device 6, a reactor 7, a condenser 9, a drying device 10, a chromatograph 11, a collection device 12, a steam generator 13, a superheater 14, a resistance furnace 15, and a piping system for connecting the devices.
Wherein, the inlet of the preheater 3 is communicated with the carrier gas storage device 1, and a flow controller 2 is arranged between the two. The carrier gas storage device 1 is used to store nitrogen gas, inert gas, etc., and the main function of the carrier gas is to carry water vapor generated by the vapor generator 13.
The outlet of the preheater 3 is respectively communicated with the inlet of a steam generator 13 and one end of a second three-way valve 5 through a first three-way valve 4, the other two ports of the second three-way valve 5 are respectively communicated with the outlet of a superheater 14 and the inlet of the reactor 7, and the outlet of the steam generator 13 is communicated with the inlet of the superheater 14 through a pipeline. The preheater 3 and the superheater 14 both adopt an electric heating mode, and the preheater 3 preheats the carrier gas from the carrier gas storage device and then enters the steam generator 13 through the first three-way valve. The main function of the superheater 14 is to heat the water vapor to a superheat temperature.
The reactor 7 is arranged in a microwave generating device 6. Microwave radiation is input into the reaction cavity through the microwave generated by the microwave generating device 6, the reactor 7 is arranged in the reaction cavity, and a catalyst needs to be arranged in the reactor when hydrogen is prepared.
The outlet of the reactor 7, the condenser 9, the drying device 10 and the collecting device 12 are sequentially communicated through pipelines, and the chromatograph 11 is arranged on a communication pipeline between the drying device 10 and the collecting device 12. The chromatograph is used for detecting the components of the generated mixed gas, and the hydrogen production performance of the catalyst is effectively evaluated by accurately analyzing the product.
The high oxidation state metal oxide is subjected to thermal reduction reaction at high temperature provided by a high microwave generating device and under protective atmosphere provided by a carrier gas storage device 1 (only a path of the carrier gas storage device 1 → a flow controller 2 → a preheater 3 → a reactor 7 is formed at this time), and is pyrolyzed into low oxidation state metal oxide and oxygen, and the oxygen enters a collecting device 12 to be collected after passing through a condenser 9 and a drying device 10 in sequence. Then the low oxidation state metal oxide is continuously hydrolyzed with superheated steam at a lower temperature to generate hydrogen and oxidized into high oxidation state metal oxide (at this time, a passage of the carrier gas storage device 1 → the flow controller 2 → the preheater 3-the steam generator 13-the superheater 14-the reactor 7 is formed).
It is understood that on the basis of the first embodiment, the following technical solutions including but not limited to the following may be derived to solve different technical problems and achieve different purposes of the invention, and specific examples are as follows:
second embodimentThe condenser is of a jacket type structure, a water inlet and a water outlet are formed in the jacket, and the circulation of the condensate in the jacket can be realized through the pumping device. The lower end of the condenser also contains a trap for storing liquid water condensed from the gaseous products. Because oxygen/hydrogen from the reactor is generated at high temperature in the reaction process, the gases need to be collected after being cooled, and the safety of gas storage is ensured; in addition, the hydrogen gas also contains part of unreacted water vapor, so that the water vapor needs to be removed by condensation to ensure the purity of the collected hydrogen gas.
Third embodiment The drying device 10 adopts a water removal device, the water removal device is a container filled with allochroic silica gel, and the gaseous product enters the water removal device under the pushing of carrier gas to realize dehydration. Because the superheated steam is required to react with the low-oxidation-state metal oxide in the hydrolysis reaction for producing hydrogen, the obtained hydrogen contains unreacted steam, and a drying device is further required to be adopted to ensure the hydrogen drying after condensation in order to ensure the purity of the collected hydrogen.
Fourth embodimentThe reactor is made of quartz, and is required to be capable of bearing the reaction because the reactor is a place for providing thermal reduction reactionThe required temperature environment and the high temperature resistance of the quartz can well meet the conditions.
Fifth embodimentAnd the connecting pipeline of the reactor inlet and the superheater outlet is provided with a heat insulation material. The unnecessary dissipation of heat energy by the reactor inlet and superheater outlet connecting pipes can be prevented; the heat-insulating material is made of quartz heat-insulating cotton.
Sixth embodimentThe hydrogen plant also comprises an electric resistance furnace 15 for heating the reactor 7 in the hydrolysis reaction. The high oxidation state metal oxide is subjected to thermal reduction reaction at high temperature provided by a high microwave generating device, and is pyrolyzed into low oxidation state metal oxide and oxygen, and the oxygen sequentially passes through a condenser 9 and a drying device 10 and then enters a collecting device 12 for collection. The loaded low oxidation state metal oxide is then placed in a resistance furnace 15 where it reacts with water at a relatively low temperature to produce hydrogen and is oxidized to a high oxidation state metal oxide (hydrolysis reaction).
Seventh embodimentThe preparation of the wave-absorbing catalyst comprises the following steps:
(1) weighing a precursor compound of a redox active substance: mg (NO)3)2·6H2O、Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Fe(NO3)3·9H2And O, and weighing four metal cations according to equimolar ratio (0.01 mol in all). Then, the weighed precursor compound of the redox active substance was dissolved in ionic water 4 times the mass of the precursor compound, and stirred with a glass rod for 300 revolutions to form an aqueous suspension solution.
(2) Adding Ethylene Diamine Tetraacetic Acid (EDTA) and citric acid into the aqueous suspension solution obtained in the step (1), and uniformly stirring with a glass rod; the Ethylene Diamine Tetraacetic Acid (EDTA) and the citric acid respectively account for 60% and 75% of the total molar amount of the metal cations.
(3) And (3) adjusting the pH value of the aqueous suspension solution prepared in the step (2) to 11 by using a 1mol/L NaOH solution, and enabling the solution to become dark brown for later use.
(4) And (4) putting the dark brown solution obtained in the step (3) into a water bath kettle at the temperature of 90 ℃, and stirring to evaporate water until the solution becomes a colloid.
(5) Weighing and recording the mass of the porous silicon carbide ceramic foam (shown in the left picture in figure 2), putting the porous silicon carbide ceramic foam into the colloidal solution obtained in the step (4), and uniformly coating the porous silicon carbide ceramic foam; then the porous silicon carbide ceramic foam is placed in an electric heating constant-temperature drying oven, the drying temperature is set to be 150 ℃, and the porous silicon carbide ceramic foam is dried overnight.
(6) Placing the porous silicon carbide ceramic foam obtained after drying in the step (5) in a quartz reactor, and then placing the reactor in a reaction cavity of a microwave generating device for calcining to convert a precursor compound of a redox active substance into a corresponding metal oxide (catalyst); setting the power of a microwave generating device at 900W, calcining for 30min, and introducing nitrogen gas of 300ml/min into the reactor all the time in the calcining process.
(8) After the reactor is cooled to normal temperature, taking out the silicon carbide ceramic foam loaded with the catalyst, weighing and calculating to obtain the load capacity, thus obtaining the wave-absorbing catalyst (FeCoMgNi) OxSilicon carbide ceramic foam) as shown in the right diagram of fig. 2, it can be seen that the silicon carbide ceramic foam is loaded with black high oxidation state metal oxide (fecormni) Ox。
Furthermore, the invention also performs a thermochemical hydrogen production test based on microwave heating by using the hydrogen production device shown in the above embodiment, which is concretely as follows.
Eighth embodimentThe thermochemical hydrogen production method based on microwave heating comprises the following steps:
(1) the catalyst prepared in the seventh example (supporting about 2g of (FeCoMgNi) OxSilicon carbide ceramic foam) is placed in a reactor 7, the reactor is placed in a microwave generating device 6, the temperature of a preheater 3 is set to 50 ℃, the temperature of a steam generator 13 is set to 80 ℃, the temperature of a superheater is set to 200 ℃, a first three-way valve 4 and a second three-way valve 5 are opened, a path of a carrier gas storage device 1 → a flow controller 2 → the preheater 3 → the reactor 7 is formed, and a thermal reduction reaction is prepared.
(2) And when the temperatures of the preheater 3, the steam generator 13 and the superheater reach the preset values, opening an air outlet valve of the carrier gas storage device 1, setting the flow of the flow controller 2 to be 300ml/min, purging the reaction system by using nitrogen for 5min, discharging air in the reaction system, and filling the reaction system with nitrogen.
(3) Setting the power of a microwave generating device 6 to be 900W, heating for 3min, and loading high oxidation state metal oxide (FeCoMgNi) O on the silicon carbide ceramic foam in the protective atmosphere provided by nitrogenxCarrying out thermal reduction reaction, pyrolyzing the mixture into low oxidation state metal oxide and oxygen, and collecting the oxygen by a collecting device 12 after the oxygen sequentially passes through a cooling device 9 and a drying water device 10; the chromatograph 11 detects the mixed gas component.
(4) After the thermal reduction reaction is finished, setting the microwave power to be 900W, heating for 20min, adjusting the first three-way valve 4 and the second three-way valve 5 to form a channel of a carrier gas storage device 1 → a flow controller 2 → a preheater 3-a steam generator 13-a superheater 14-a reactor 7, operating a microwave generating device to perform hydrolysis reaction, sequentially passing hydrogen generated by the reaction and unreacted steam through a cooling device 9, collecting the hydrogen and unreacted steam by a collecting device 12 after a drying device 10, and detecting the components of the mixed gas by a chromatograph 11.
(5) And (5) repeating the steps (1) to (4) and summarizing the data obtained by 5 times of circulation. Specifically, the cycle process is realized by the cyclic conversion of the high oxidation state metal oxide and the low oxidation state metal oxide in the reactor, that is, after the high oxidation state metal oxide generated by the hydrolysis reaction is pyrolyzed at high temperature into the low oxidation state metal oxide and oxygen, the low oxidation state metal oxide is continuously subjected to the hydrolysis reaction, and once the continuous generation process of hydrogen is completed, the cycle process is recorded as one cycle.
Ninth embodimentA thermochemical hydrogen production method based on microwave heating, which is different from the eighth embodiment in that: setting the power of a microwave generating device to 700W in the step (3), and setting the microwave power to 700W and the heating time to 30min after the thermal reduction reaction is finished in the step (4).
Tenth embodimentIn the method for thermochemically producing hydrogen based on microwave heating, as in the eighth embodiment, the power of the microwave generator is set to 500W in step (3), the microwave power is set to 500W after the thermal reduction reaction is finished in step (4), and the heating time is 30 min.
FIG. 3 is the data of the hydrogen and oxygen concentration variation and the resulting hydrogen production yield of the hydrogen production reaction by 5 thermochemical cycles of decomposing water under 900W conditions in the eighth example. As can be seen, the hydrogen production under the condition can be continued for about 20min, the peak value of the yield is 27.3 +/-1.5 ml/g, and the yield is stabilized to be about 15ml/g after 5 times of circulation.
Further, by adjusting the microwave power to 700W (as shown in FIG. 4) and 500W (as shown in FIG. 5), the hydrolysis process was continued for 30 minutes with peak hydrogen yields of 122. + -.5 ml/g and 67.7. + -.4 ml/g, respectively, much higher than that obtained with 900W. The hydrogen production was stabilized at around 40ml/g for 5 cycles at 700W and during the second cycle at maximum production there was an intense discharge that enhanced the water decomposition resulting in a significant improvement in hydrogen production and duration. While the hydrogen yield stabilized around 33ml/g for 5 cycles at 500W, about 315ml of hydrogen per gram of catalyst was produced for 5 cycles (120 min).
As shown in fig. 6, the left graph shows the catalyst supported on the silicon carbide ceramic foam which has not been used in the eighth example, and it can be seen that the catalyst is loose and has small particles. The catalyst still remained in a small particle state after three cycles under the condition of 700W, no obvious sintering phenomenon exists, and the hydrogen production activity of the catalyst in the fourth cycle is still high (as shown in figure 4).
Eleventh embodimentA thermochemical hydrogen production method based on microwave heating, which is different from the eighth embodiment in that: in the step (4), after the thermal reduction reaction is finished, the reactor 7 and the communication pipeline are transferred to the resistance furnace 15, the operating temperature of the resistance furnace is set to 800 ℃, that is, in the embodiment, the resistance furnace is used for heating the low oxidation state metal oxide generated in the reactor as a heat source instead of microwave heating, and the hydrolysis reaction is carried out on the water vapor to produce hydrogen.
Twelfth embodimentA thermochemical hydrogen production method based on microwave heating, which is different from the eleventh embodiment in that: and (5) repeating the steps (1) to (5), and setting the power of the microwave generating device to be 700W in the step (3).
Thirteenth group of inventionsExamplesA thermochemical hydrogen production method based on microwave heating, which is different from the eleventh embodiment in that: and (5) repeating the steps (1) to (5), and setting the power of the microwave generating device to be 500W in the step (3).
In addition, it can be seen from the above examples that the thermal reduction time is only 3 to 5min (as in step (3) of the eighth example) when the hydrogen production apparatus and method of the present invention are used. And the hydrogen production amount is high under the condition of microwave equal power, the catalyst has good activity and durability, the system balance time is short, the operation is stable, and the error of output data is small. Compared with a solar light-gathering simulator and the traditional heating equipment, the hydrogen production device and the method have long operation time and high cost, and have more outstanding technical advantages.
In the previous description, numerous specific details were set forth in order to provide a thorough understanding of the present invention. The foregoing description is only a preferred embodiment of the invention, which can be embodied in many different forms than described herein, and therefore the invention is not limited to the specific embodiments disclosed above. And that those skilled in the art may, using the methods and techniques disclosed above, make numerous possible variations and modifications to the disclosed embodiments, or modify equivalents thereof, without departing from the scope of the claimed embodiments. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A thermochemical hydrogen production system based on microwave heating, comprising:
the inlet of the preheater is communicated with the carrier gas storage device, and a flow controller is arranged between the inlet of the preheater and the carrier gas storage device;
the outlet of the preheater is respectively communicated with the inlet of the steam generator and one port of the second three-way valve through a first three-way valve; the other two ports of the second three-way valve are respectively communicated with the outlet of the superheater and the inlet of the reactor;
the reactor is arranged in the microwave generating device; the outlet of the steam generator is communicated with the inlet of the superheater through a pipeline;
the outlet of the reactor, the condenser, the drying device and the collecting device are communicated in sequence;
the chromatograph is arranged on a communication pipeline between the drying device and the collecting device.
2. A microwave heating-based thermochemical hydrogen production system of claim 1 wherein the carrier gas in the carrier gas storage device is an inert gas or nitrogen;
or the material of the reactor is high-temperature-resistant quartz;
or the microwave generated by the microwave generating device inputs microwave radiation into the reaction cavity through the waveguide, and the reactor is arranged in the reaction cavity;
or both the preheater and the superheater are electrically heated;
alternatively, the steam generator is a device that heats water through a water bath or oil bath.
3. A microwave heating-based thermochemical hydrogen production system of claim 1 wherein the drying means employs a water removal means; preferably, the water removal device is a container filled with allochroic silica gel;
or the connecting pipeline of the reactor inlet and the superheater outlet is provided with a heat insulation material;
or the condenser is of a jacket type structure and can realize condensate circulation by a pumping device; preferably, the condenser further comprises a trap.
4. A microwave heating-based thermochemical hydrogen production system of any of claims 1 to 3 further comprising an electric resistance furnace for heating the reactor in the hydrolysis reaction.
5. A thermochemical hydrogen production method based on microwave heating, characterized by being carried out by using the thermochemical hydrogen production apparatus according to any of claims 1 to 3, and comprising the following steps:
(1) putting a catalyst into a reactor, placing the reactor into a reaction cavity of a microwave generating device, ensuring the sealing property of a communicating pipeline, opening all valves of a three-way valve, opening carrier gas and setting the flow of the carrier gas to purge each part of the system;
(2) adjusting the state of the three-way valve, only forming a carrier gas storage device → a flow controller → a preheater → a reactor passage, and opening the preheater/steam generator/superheater until the preheater/steam generator/superheater reaches a preset temperature;
(3) setting the heating power and the heating time of a microwave generating device, and operating the microwave generating device to perform thermal reduction reaction after the preheater/steam generator/superheater reaches a preset temperature;
(4) after the thermal reduction reaction is finished, adjusting the state of a three-way valve to form a carrier gas storage device → a flow controller → a preheater-steam generator-superheater-reactor passage, setting microwave heating power and heating time, and operating a microwave generating device to perform hydrolysis reaction;
(5) the cooled and dried gaseous product was analyzed by detection in a chromatograph.
6. A thermochemical hydrogen production method based on microwave heating, characterized by being carried out by using the thermochemical hydrogen production apparatus of claim 4, and comprising the following steps:
(1) putting a catalyst into a reactor, placing the reactor into a reaction cavity of a microwave generating device, ensuring the sealing property of a communicating pipeline, opening all valves of a three-way valve, opening carrier gas and setting the flow of the carrier gas to purge each part of the system;
(2) adjusting the state of the three-way valve, only forming a carrier gas storage device → a flow controller → a preheater → a reactor passage, and opening the preheater/superheater until the preheater/superheater reaches a preset temperature;
(3) setting the heating power and the heating time of a microwave generating device, and operating the microwave generating device to perform thermal reduction reaction after the preheater/superheater reaches a preset temperature;
(4) after the thermal reduction reaction is finished, transferring the reactor and the connecting pipeline thereof to a resistance furnace, opening the steam generator/resistance furnace, and waiting for the steam generator/resistance furnace to reach a preset temperature;
(5) when the steam generator/resistance furnace reaches a preset temperature, adjusting the state of the three-way valve to form a carrier gas storage device → a flow controller → a preheater-steam generator-superheater-reactor channel for hydrolysis reaction;
(6) the cooled and dried gaseous product was analyzed by detection in a chromatograph.
7. A microwave heating-based thermochemical hydrogen production method according to claim 5, wherein when thermochemical water splitting is performed by using a microwave generator to produce hydrogen, oxidation and reduction reactions are performed under microwave equipower conditions, and continuous regeneration of hydrogen is realized.
8. A microwave heating-based thermochemical hydrogen production method according to claim 5, wherein when thermochemical water splitting is performed by using a microwave generator to produce hydrogen, oxidation and reduction reactions are performed under the microwave variable power condition, that is, the oxidation reaction is performed at a higher power, and the hydrolysis reaction is performed at a lower power, so that continuous regeneration of hydrogen is realized.
9. A thermochemical hydrogen production process based on microwave heating according to any of claims 5 to 8, whereby the catalyst is a metal oxide supported on a porous wave-absorbing matrix, or a metal oxide doped with a strongly wave-absorbing substance, or a metal oxide pressed to have a porous structure; preferably, the metal oxide includes iron-based oxides, cerium-based oxides, and perovskite-type oxides; preferably, the wave-absorbing matrix comprises porous silicon carbide ceramic foam.
10. Use of a microwave heating-based thermochemical hydrogen production system according to any of claims 1 to 4 and/or a microwave heating-based thermochemical hydrogen production method according to any of claims 5 to 9 in the field of energy.
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| CN113772627A (en) * | 2021-10-11 | 2021-12-10 | 山东大学 | Method for preparing synthesis gas by microwave thermochemical methane and application |
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