CN109264670B

CN109264670B - Methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization

Info

Publication number: CN109264670B
Application number: CN201811430210.9A
Authority: CN
Inventors: 张家盛; 彭隆肇; 王�锋; 王国强; 丁佳渝; 姚凌
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-11-28
Filing date: 2018-11-28
Publication date: 2022-04-19
Anticipated expiration: 2038-11-28
Also published as: CN109264670A

Abstract

The invention discloses a methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization, which comprises a raw material box, a pump, a gasification device, a main reaction device, a gas treatment device and a gas storage device which are sequentially connected in series through pipelines; the gasification device comprises a gasification pipe, a coil I wound outside the gasification pipe, a photovoltaic power generation panel I and an electromagnetic controller I used for controlling electric energy generated by the photovoltaic power generation panel I to be input into the coil I; the main reaction device comprises a main reaction tube, a light gathering plate, metal particles, a coil II, a photovoltaic power generation plate II and an electromagnetic controller II, wherein the light gathering plate is used for gathering sunlight to the main reaction tube, the metal particles are coated on the cold spot position of the reaction tube, the coil II is used for carrying out induction heating on the metal particles, and the electromagnetic controller II is used for controlling electric energy generated by the photovoltaic power generation plate II to be input into the coil II; the reactor of the invention can improve the temperature distribution in the reaction, and can also dynamically adjust the temperature condition, improve the reaction efficiency, optimize the energy utilization condition, improve the yield of hydrogen and the like.

Description

Methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization

Technical Field

The invention relates to the technical field of solar photoelectric photo-thermal methanol reforming, in particular to a methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization.

Background

Solar energy is a primary energy, and the problems of grid connection, power transmission and the like are solved by using the solar energy for power generation. Hydrogen is widely applied to industry and life nowadays due to the advantages of high energy density, convenience in transportation and the like, so that the hydrogen production by utilizing solar energy to catalyze methanol reforming is an important way for reasonably utilizing solar energy at present. The hydrogen production by reforming the solar methanol belongs to the solar thermochemical hydrogen production, and the fuel reforming is a heterogeneous catalytic reaction process which is generated in a reformer. Reactant molecules from the main fluid are adsorbed on the surfaces of catalyst particles after being diffused outwards, and then are diffused inwards to active sites of the catalyst to rapidly perform catalytic reaction. However, the rate of the reforming reaction is much higher than the rate of molecular diffusion, which causes the majority of the molecules in any cluster at the inlet of the reformer to chemically react at the inlet of the bed, and the number of molecules reaching the back of the bed drops dramatically. This results in many catalysts failing to perform their catalytic function and reactants already flowing out of the reactor, thereby reducing the efficiency of the catalyst. More importantly, methanol steam reforming is a strongly endothermic process, which necessarily increases the endotherm of the reaction at the inlet. Due to the heat transfer limitations of the reactor (such as thermal contact resistance between catalyst particles and the wall surface of the reactor, between catalyst particles, etc.), the endothermic heat of the reaction cannot be sufficiently supplied, so that the endothermic reaction causes a temperature drop, cold spots are formed, a temperature gradient occurs in the whole bed, and the temperature gradient at the inlet is the largest. Under the action of the temperature gradient, the temperature of partial catalyst or even most catalyst can not reach the optimum operation temperature. The activity of the catalyst cannot be fully exerted, and the effective utilization rate of the catalyst is further reduced, so that the hydrogen production efficiency is influenced. This cold spot temperature gradient eventually leads to a decrease in the stability and lifetime of the catalyst and compromises the reactor materials.

Disclosure of Invention

In order to make up for the defects of the prior art, the invention provides a solar reforming hydrogen production reactor based on electromagnetic induction heating. It can improve the temperature distribution in the reaction, and also can dynamically adjust the temperature condition, improve the reaction efficiency, optimize the energy utilization condition, improve the hydrogen yield, and the like, thereby being an ideal methanol reforming reactor.

The invention relates to a methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization, which comprises a raw material box, a pump, a gasification device, a main reaction device, a gas treatment device and a gas storage device which are sequentially connected in series through pipelines; the gasification device comprises a gasification pipe, a coil I wound outside the gasification pipe, a photovoltaic power generation panel I and an electromagnetic controller I used for controlling electric energy generated by the photovoltaic power generation panel I to be input into the coil I; the main reaction device comprises a main reaction tube, a light gathering plate, metal particles, a coil II, a photovoltaic power generation plate II and an electromagnetic controller II, wherein the light gathering plate is used for gathering sunlight to the main reaction tube, the metal particles are coated on the cold spot position of the reaction tube, the coil II is used for carrying out induction heating on the metal particles, and the electromagnetic controller II is used for controlling electric energy generated by the photovoltaic power generation plate II to be input into the coil II;

further, the outer surface of the metal particle is coated with a catalyst coating layer;

further, the gasification pipe and the main reaction pipe are both wrapped by heat-insulating asbestos to prevent heat loss;

the device further comprises a temperature thermocouple I for detecting the temperature of the gas discharged by the gasification pipe and a temperature thermocouple II for detecting the temperature of the gas discharged by the main reaction pipe;

further, a three-way valve is arranged at the tail end of the gasification pipe;

furthermore, the caliber of the air inlet of the main reaction tube is gradually increased from front to back, and a sand core for stabilizing gas is arranged in the air inlet;

further, the coil I is an annular winding coil, and the coil II comprises a plurality of groups of disk-shaped winding coils with sequentially reduced densities and connected in series;

further, the gasification pipe comprises a stainless steel inner pipe and an iron outer pipe, the gasification pipe is of a bent structure, and the caliber of an air inlet of the gasification pipe is gradually reduced from front to back;

further, the solar panel is equipped with the polylith, and it distributes along main reaction tube length direction, and the width of solar panel reduces along the gas flow direction gradually, and the light of its gathering is the straight line along main reaction tube longitudinal extension.

The invention has the beneficial effects that: the reaction device and the accessory device are connected to form the complete methanol reforming reaction device, the reforming system carries out the solar methanol reforming hydrogen production reaction in a place with sufficient solar illumination, the temperature distribution of the product in the tube is more uniform under the condition of better illumination intensity, and the service life of the reaction tube is prolonged; the reaction can still be normally carried out when the illumination condition is not good, the reforming reaction is more suitable to be stably carried out, the utilization rate of the catalyst is improved, and the yield of hydrogen is improved. The whole structure optimization by utilizing electromagnetic induction photo-thermal photoelectricity also improves the reaction efficiency, so that the reactor is more suitable for the working environment with larger change.

Drawings

The invention is further described below with reference to the following figures and examples:

FIG. 1 is a flow chart of the operation of a reaction apparatus;

FIG. 2 is a front view showing the connection between the gasification tube and the main reaction tube;

FIG. 3 is a schematic view of the combination of the light-gathering plate and the main reaction tube;

fig. 4 is an overall perspective view of the asbestos insulation layer and the disc-shaped wound coil.

Detailed Description

The methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization of the embodiment comprises a raw material tank 16, a pump 20, a gasification device, a main reaction device, a gas treatment device and a gas storage device 18 which are sequentially connected in series through pipelines; the gasification device comprises a gasification pipe 5, a coil I wound outside the gasification pipe 5, a photovoltaic power generation panel I and an electromagnetic controller I2 used for controlling electric energy generated by the photovoltaic power generation panel I3 to be input into the coil I; the main reaction device comprises a main reaction tube 11, a light gathering plate 1 for gathering sunlight on the main reaction tube 11, metal particles coated at the cold spot position of the reaction tube 11, a coil II for carrying out induction heating on the metal particles, a photovoltaic power generation plate II 19 and an electromagnetic controller II 4 for controlling electric energy generated by the photovoltaic power generation plate II 19 to be input into the coil II; when the device works, a mixture of methanol and water is introduced into a gasification pipe 5 for reaction by using a pump 20, electric energy generated by a photovoltaic power generation plate I3 is input into an electromagnetic device, alternating current generated by the electromagnetic device is transmitted to a coil I in the gasification pipe 5, the temperature of the metal gasification pipe 5 is raised to heat and gasify the passing methanol-water mixture into superheated steam, then the superheated steam flows into a main reaction pipe 11, sunlight is gathered below the main reaction pipe 11 by a parabolic light gathering plate 1 to raise the temperature below the main reaction pipe 11, metal particles coated with a catalyst are added at a cold spot of the reaction pipe 11 for further improving the cold spot, the electric energy generated by photovoltaic generates high-frequency alternating current through an electromagnetic induction mainboard, and the alternating current is input into a coil II to heat the metal particles in the main reaction pipe 11 to serve as an internal heat source for heating the cold spot. The coil II on the upper side of the main reaction tube 11 is wrapped by asbestos 8 to prevent heat loss. A copper-based catalyst is placed in the tube, superheated steam of methanol and water flows through the main reaction tube 11, a reforming reaction occurs in the main reaction tube 11, and finally, reacted gas is discharged from an outlet at the rear of the reaction tube 11; in addition, a temperature thermocouple I14 is arranged behind the gasification tube 5 and used for monitoring the gas temperature at the front section of the reaction tube. The gasification end is connected with a three-way valve 10, a front temperature thermocouple 14 is observed, when the temperature is not high enough, the three-way valve 10 is adjusted to discharge the gas, the gas is gasified properly and fully, and then the rear three-way valve 10 is adjusted to lead the gas to enter a main reaction tube 11 for the next reforming reaction. The sand core is welded in the middle of the glass air inlet 12 with a small front part and a large back part to play a role in stabilizing gas, gasified reactants enter the reaction tube to react, and the temperature measuring thermocouple II 15 is arranged at the rear end of the reaction tube to monitor the temperature of the reacted gas. The gas is then introduced into the gas treatment device 17 and the gas collection device 18 to complete the reaction.

The gasification pipe 5 in the embodiment is of a bent structure with a thick front part and a thin rear part, the outer layer of the gasification pipe is a heat-insulating asbestos layer 8, the outer layer of the heat-insulating layer is provided with an annular winding coil 7 (namely a coil I), the temperature of the gasification pipe 5 is increased under the control of an electromagnetic induction controller I2, a flowing methanol and water mixture is heated, heated and gasified into superheated steam, the superheated steam flows out of the gasification pipe 5 through a pipeline, and a three-way valve 10 is arranged at the tail end of the gasification pipe 5. The rear end of the three-way valve 10 is communicated with an air inlet 12 of a main glass reaction tube 11, and the tail end of the main glass reaction tube 11 is connected with a glass air outlet 13. The inner layer of the gasification pipe 5 is made of stainless steel, the outer layer is made of ferrous metal, and the metal in the gasification pipe is heated by the annular winding coil 7 (namely the coil I) to rapidly rise the temperature, so that the passing liquid is gasified and overheated after flowing through the gasification pipe 5. The three-way valve 10 controls the flow of gas and liquid, when the gasification is not complete at the beginning, the three-way valve 10 is communicated with the outside to discharge the gas-liquid mixture which is not completely gasified. After the gasification is completed, the three-way valve 10 is communicated with the gas inlet 12 of the reaction tube 11, the overheated gas flows into the reaction tube 11, the design of the three-way valve 10 ensures that the reaction gas is introduced into the reaction tube 11, the reaction tube 11 is protected, and the service life of the reaction tube 11 is prolonged.

As shown in fig. 3, the lower part of the glass main reaction tube 11 is provided with four parabolic light collecting plates 1 with gradually reduced width along the gas flow direction, the four parabolic light collecting plates are supported below the main reaction tube 11 through a bracket, the light collecting plates 1 collect sunlight on the lower part of the reaction tube 11, the energy is changed from high to low along the axial direction, and the energy is highest at the cold spot of the reaction tube 11. When the device is debugged, the reflector is fixed firstly, and then the reactor is fixed, so that the light rays are ensured to be converged into a line and be fully absorbed by the reactor. The light energy is mainly gathered to the surface of the lower part of the reaction tube 11 in the form of heat energy, and is transmitted to the inside of the glass tube through heat conduction and then is transmitted to the flowing working medium inside in the form of convection heat transmission. The external heating mode has large energy loss, the wide design and the narrow design improve the condition of temperature unevenness due to the characteristics of reaction, but the cold spot effect still exists, so the structure of the reaction tube 11 needs to be optimized by combining the electromagnetic internal heating mode.

As shown in fig. 4, a disc-shaped winding coil 6 (i.e., coil ii) is partially installed on the reaction tube 11, and the coil is externally wrapped by an insulating asbestos layer 9. The disk-shaped wound coil is wound long in the axial direction of the reaction tube 11 and is elongated to ensure the installation in the reaction tube 11. The disc-shaped coils are provided with three groups, three groups of coils are connected in series, the first group has the most dense winding density, the second group has the least dense winding density, and the last group has the least dense winding density. The arrangement can make the metal in the front section heat up more quickly and optimize the temperature condition at the cold point. After the disc-shaped winding coil 6 is electrified with alternating current, the metal coated with the catalyst in the reaction tube 11 generates skin effect, the temperature is rapidly increased, and heat is transferred to the reactant through the catalyst conducted to the outside and then through convection heat exchange. Therefore, the internal heating mode is fast in temperature rise, convenient to control, capable of reducing heat loss and good in energy utilization. The mode that photoelectric light and heat coupling got up like this utilizes the photoelectricity to turn into electromagnetic heating internal energy with the insufficient condition of light and heat and supplements, has solved the influence that the cold spot brought.

The tubular reactor for reforming the solar photoelectric photo-thermal methanol not only serves as a reaction device, but also is provided with the gasification tube 5 with electromagnetic induction at the front end, so that electromagnetic heating, gasification and reaction are integrated, the volume of the device is greatly simplified, and the structure of the reaction tube 11 is improved. And the main reaction tube 11 adopts the design of a glass tube, and the effect of the gasified steam can be visually seen, so that the incomplete gasification condition is reduced, and the normal operation of the experiment is ensured. The mode of internal heating after photoelectric conversion, the mode of external heating of coupling light and heat can also greatly improve the cold spot condition, the reaction temperature distribution is more reasonable, the catalyst utilization rate is higher, and the hydrogen yield is also improved. The green and environment-friendly solar energy is used as an energy source, so that the energy is saved, and the low-grade energy is stored and utilized more reasonably by saving the resource.

When the device is used for reforming methanol, the condition of electromagnetic induction heating can be changed through the local weather condition, the flow of introduced gas can be increased when the illumination intensity is strong enough, and the power of electromagnetic induction heating is changed to achieve a better hydrogen production effect. When the illumination intensity is not intense enough, the required heat can be supplemented by increasing the power of electromagnetic induction and utilizing an internal heating mode of electromagnetic induction. Therefore, the reaction rate can be controlled through the flow, and the reaction temperature can be adjusted by utilizing a coupled electromagnetic heating mode, so that the reaction rate is controlled. The solar energy photo-thermal and photoelectric coupling is achieved, photo-electricity supplements the photo-thermal problem of poor cold spot, the heating mode of electromagnetic induction internal heating is used, waste of electric energy is greatly reduced, and compared with grid-connected power transmission and supply, energy utilization is more reasonable.

Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims

1. A methanol reforming hydrogen production reactor based on solar thermoelectric comprehensive utilization is characterized in that: comprises a raw material box, a pump, a gasification device, a main reaction device, a gas treatment device and a gas storage device which are sequentially connected in series through pipelines;

the main reaction device comprises a main reaction tube, a light gathering plate, metal particles, a coil II, a photovoltaic power generation plate II and an electromagnetic controller II, wherein the light gathering plate is used for gathering sunlight to the main reaction tube, the metal particles are coated at the cold spot position of the reaction tube, the coil II is used for carrying out induction heating on the metal particles, and the electromagnetic controller II is used for controlling electric energy generated by the photovoltaic power generation plate II to be input into the coil II; the outer surface of the metal particle is coated with a catalyst coating; the light collecting plates are four parabolic light collecting plates with the width gradually reduced along the gas flowing direction, the parabolic light collecting plates are supported below the main reaction tube through a support, sunlight is collected at the lower part of the reaction tube by the light collecting plates, the energy is changed from high to low along the axial direction, and the energy is highest at the cold point of the reaction tube;

the gasification device comprises a gasification pipe, a coil I wound outside the gasification pipe, a photovoltaic power generation panel I and an electromagnetic controller I used for controlling electric energy generated by the photovoltaic power generation panel I to be input into the coil I; the device also comprises a temperature thermocouple I for detecting the temperature of the gas discharged by the gasification pipe and a temperature thermocouple II for detecting the temperature of the gas discharged by the main reaction pipe;

coil I is annular winding coil, and coil II includes that multiunit density reduces in proper order and the disc winding coil of establishing ties each other.

2. The methanol reforming hydrogen production reactor based on solar thermal power integrated utilization according to claim 1, characterized in that: the gasification pipe and the main reaction pipe are both wrapped by heat-insulating asbestos to prevent heat loss.

3. The methanol reforming hydrogen production reactor based on solar thermal power integrated utilization according to claim 2, characterized in that: the tail end of the gasification pipe is provided with a three-way valve.

4. The methanol reforming hydrogen production reactor based on solar thermal power integrated utilization according to claim 3, characterized in that: the aperture of the air inlet of the main reaction tube is gradually increased from front to back, and a sand core for stabilizing gas is arranged in the air inlet.

5. The methanol reforming hydrogen production reactor based on solar thermal power integrated utilization according to claim 4, characterized in that: the gasification pipe comprises a stainless steel inner pipe and an iron outer pipe, the gasification pipe is of a bent structure, and the caliber of an air inlet of the gasification pipe is gradually reduced from front to back.

6. The methanol reforming hydrogen production reactor based on solar thermal power integrated utilization according to claim 5, characterized in that: the solar panel is equipped with the polylith, and it distributes along main reaction tube length direction, and the width of solar panel reduces along gas flow direction gradually, and the light of its gathering is the straight line along main reaction tube longitudinal extension.