CN113856562A - Circulating reaction system for liquid organic matter hydrogenation - Google Patents
Circulating reaction system for liquid organic matter hydrogenation Download PDFInfo
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- CN113856562A CN113856562A CN202111279014.8A CN202111279014A CN113856562A CN 113856562 A CN113856562 A CN 113856562A CN 202111279014 A CN202111279014 A CN 202111279014A CN 113856562 A CN113856562 A CN 113856562A
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
The invention relates to a circulating reaction system for hydrogenation of liquid organic matters, and belongs to the technical field of hydrogen energy storage and transportation. In the circulating reaction system, a liquid outlet of a normal pressure medium tank is connected with a liquid inlet of the pressure reactor, and a metering pump and a liquid flow controller are arranged between the liquid outlet of the normal pressure medium tank and the liquid inlet of the pressure reactor; the gas inlet of the pressure reactor is connected with an external hydrogen source, and a gas flow controller and a hydrogen preheating device are arranged between the gas inlet of the pressure reactor and the external hydrogen source; the liquid outlet of the pressure reactor, the pressure reducing device and the liquid inlet of the normal pressure medium tank are sequentially connected; the tail gas recovery device is connected with a gas outlet of the pressure reactor. The circulation reaction system of the invention realizes the circulation of the hydrogen storage medium in the circulation reaction system, so that the hydrogen storage medium can enter the pressure reactor for many times, thereby ensuring the completion rate of hydrogenation, and the hydrogen storage medium before and after the hydrogenation reaction is stored in the same normal pressure medium tank, thereby simplifying the filling process.
Description
Technical Field
The invention relates to a circulating reaction system for hydrogenation of liquid organic matters, and belongs to the technical field of hydrogen energy storage and transportation.
Background
The liquid organic hydrogen storage technology belongs to a new energy storage technology, and a hydrogenation system used for the technology is less developed. The prior continuous hydrogenation reaction system and the hydrogenation reaction method (CN105060244A) of a liquid organic hydrogen storage carrier, which are mainly proposed by Chenghan-han Songyou of Jiangsu hydrogen and solar energy Limited company, comprise a feeding system, a preheater, a fixed bed reaction tower kettle and a separation device; the feeding system is communicated with an inlet of the preheater through a pipeline, an outlet of the preheater is communicated with an inlet of a fixed bed reaction tower kettle through a pipeline, and an outlet of the fixed bed reaction tower kettle is communicated with an inlet of the separation device through a pipeline; the fixed bed reaction tower is characterized in that a hydrogenation catalyst and an inert material are filled in the fixed bed reaction tower, and a circulating heat-conducting medium is arranged in an interlayer on the surface of the fixed bed reaction tower to keep the constant temperature in the tower. However, the hydrogenation reaction system is mainly one-way one-time hydrogenation, and two storage tanks are needed before and after the hydrogen storage medium to store the medium before and after hydrogenation respectively. Because the unidirectional hydrogenation is a one-time hydrogenation reaction, if the flow of the passing medium is too large and does not stay in the reactor, complete hydrogenation is difficult to realize in the time that the hydrogen storage medium flows through the reactor, and the unidirectional hydrogenation is not suitable for large-scale hydrogenation application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a circulating reaction system for liquid organic matter hydrogenation, which realizes the circulation of a hydrogen storage medium in the system, so that the hydrogen storage medium can enter a pressure reactor for multiple times, thereby ensuring the completion rate of hydrogenation, and the hydrogen storage medium before and after hydrogenation reaction is stored in the same normal pressure medium tank, thereby simplifying the filling process.
The purpose of the invention is realized by the following technical scheme.
A circulating reaction system for liquid organic matter hydrogenation comprises a normal pressure medium tank, a metering pump, a liquid flow controller, a pressure reactor, a gas flow controller, a hydrogen preheating device, a pressure reducing device and a tail gas recovery device;
the upper part of the normal pressure medium tank is provided with a liquid inlet, and the lower part of the normal pressure medium tank is provided with a liquid outlet;
the metering pump is a pump with a buffer device (such as a buffer column) to ensure the stable liquid flow;
the pressure reactor is a reaction vessel containing a heating device, the upper part of the pressure reactor is provided with a liquid inlet and a gas outlet, and the lower part of the pressure reactor is provided with a gas inlet and a liquid outlet;
a liquid outlet of the normal pressure medium tank is connected with a liquid inlet of the pressure reactor, and a metering pump and a liquid flow controller are arranged on a pipeline which connects the liquid outlet of the normal pressure medium tank with the liquid inlet of the pressure reactor; the gas inlet of the pressure reactor is connected with an external hydrogen source, and a gas flow controller and a hydrogen preheating device are arranged on a pipeline connecting the gas inlet of the pressure reactor with the hydrogen source; the liquid outlet of the pressure reactor, the pressure reducing device and the liquid inlet of the normal pressure medium tank are sequentially connected; the tail gas recovery device is connected with a gas outlet of the pressure reactor.
The working principle of the circulation reaction system of the invention is as follows: hydrogen storage medium in the normal pressure medium tank enters the pressure reactor at a constant flow rate through a metering pump and a liquid flow controller; an external hydrogen source is preheated to a certain temperature and then enters the pressure reactor at a constant flow rate through a gas flow controller and a hydrogen preheating device; hydrogen entering the pressure reactor contacts with a hydrogen storage medium to react, liquid after the reaction flows out of the pressure reactor, returns to the normal pressure medium tank after passing through the pressure reduction device, so as to form circulation until the hydrogen storage medium in the normal pressure medium tank is fully hydrogenated, and then the normal pressure medium tank is replaced to carry out a new round of hydrogenation reaction; in addition, the incompletely reacted hydrogen in the pressure reactor enters a tail gas recovery device from an upper gas outlet for recycling or emptying.
Further, the heating device in the pressure reactor is an oil bath jacket or an electric heater, and the heating device is installed outside the reaction vessel.
Further, the tail gas recovery device comprises a condenser and a hydrogen storage tank; one end of the condenser is connected with a gas outlet of the pressure reactor, and the other end of the condenser is connected with the hydrogen storage tank.
Further, in the hydrogenation reaction process, the reaction temperature in the pressure reactor is 80-150 ℃, and the reaction pressure is 2 MP-6 MPa; correspondingly, an external hydrogen source is preheated to 80-150 ℃ by a hydrogen preheating device before entering the pressure reactor.
Furthermore, 5-20 layers of catalytic bed layers are arranged in the pressure reactor, and the height of the catalyst filled in each layer of catalytic bed layer is preferably 50-60% of the height of the catalytic bed layer; and a gas distributor is arranged below the catalytic bed layer, so that the hydrogen can be uniformly dispersed in the pressure reactor and can contact with a hydrogen storage medium to react.
Further, the flow rate of the hydrogen storage medium in the normal pressure medium tank entering the pressure reactor is 1L/min-100L/min; the volume of the pressure reactor was 0.005m3～1.2m3(ii) a The flow rate of the external hydrogen source entering the pressure reactor is 5L/min-50L/min, and the specific flow rate of the hydrogen storage medium and the hydrogen can be set by referring to the stoichiometric ratio.
Has the advantages that:
the cyclic reaction system can realize cyclic hydrogenation reaction of organic matters such as p-benzene, quinoline, carbazole, pyridine, phenazine and derivatives thereof, and even if a hydrogen storage medium can enter the pressure reactor for multiple times, the completion rate of hydrogenation is guaranteed; the hydrogen storage media before and after the hydrogenation reaction are stored in the same normal pressure medium tank, the filling process is simplified, the hydrogen storage media can be sampled, analyzed and judged at any time when being stored in the normal pressure medium tank, meanwhile, the replacement operation of the normal pressure medium tank is very simple, and the operation time can be saved.
Drawings
FIG. 1 is a schematic view showing the connection of the circulation reaction system described in example 1.
The system comprises a normal pressure medium tank 1, a metering pump 2, a liquid flow controller 3, a pressure reactor 4, a gas flow controller 5, a hydrogen preheating device 6, a pressure reducing device 7 and a tail gas recovery device 8.
Detailed Description
The present invention is further illustrated by the following figures and detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
Example 1
A circulating reaction system for liquid organic matter hydrogenation comprises a normal pressure medium tank 1, a metering pump 2, a liquid flow controller 3, a pressure reactor 4, a gas flow controller 5, a hydrogen preheating device 6, a pressure reducing device 7 and a tail gas recovery device 8, and is shown in figure 1;
the upper part of the normal pressure medium tank 1 is provided with a liquid inlet, and the lower part is provided with a liquid outlet;
the metering pump 2 is a pump with a buffer device to ensure the stable liquid flow;
the pressure reactor 4 is a cylindrical reaction vessel of which the outer wall is provided with an oil bath jacket, the diameter is 100mm, the volume is 10L, 5 layers of catalytic bed layers are arranged in the pressure reactor, a gas distributor is also arranged below the catalytic bed layers, and the height of the catalyst filled in each layer of catalytic bed layer is 50 percent of the height of the catalytic bed layer; the upper part of the pressure reactor 4 is provided with a liquid inlet, a gas outlet, a temperature measuring port, a pressure measuring port and a safety valve interface, and the lower part of the pressure reactor 4 is provided with a gas inlet and a liquid outlet;
the tail gas recovery device 8 consists of a condenser and a hydrogen storage tank and is used for recovering hydrogen which is not completely reacted;
the liquid outlet of the normal pressure medium tank 1, the metering pump 2, the liquid flow controller 3 and the liquid inlet of the pressure reactor 4 are sequentially connected; an external hydrogen source, a gas flow controller 5, a hydrogen preheating device 6 and a gas inlet of the pressure reactor 4 are sequentially connected; the liquid outlet of the pressure reactor 4, the pressure reducing device 7 and the liquid inlet of the normal pressure medium tank 1 are sequentially connected; condenser one end and the gas outlet of pressure reactor 4 among the tail gas recovery device 8 are connected, and the condenser other end among the tail gas recovery device 8 is connected with the hydrogen holding vessel among the tail gas recovery device 8.
N-ethyl carbazole is used as a hydrogen storage medium, and NiO/Al is selected as a catalyst2O3Catalyst pellets, hydrogenation using said cyclic reaction systemThe reaction was carried out as follows: hydrogen storage media in the normal pressure medium tank 1 enter the pressure reactor 4 at a constant flow rate of 2L/min through a metering pump 2 and a liquid flow controller 3; an external hydrogen source is preheated to 130 ℃ through a gas flow controller 5 and a hydrogen preheating device 6 and then enters a pressure reactor 4 at a constant flow rate of 10L/min; hydrogen entering a pressure reactor 4 is contacted with a hydrogen storage medium, hydrogenation reaction is carried out at the reaction temperature of 130 ℃ and the reaction pressure of 3MPa, liquid after reaction flows out of the pressure reactor 4, the pressure is reduced from 3MPa to normal pressure through a pressure reducing device 7 and then returns to a normal pressure medium tank 1, circulation is formed, the hydrogen storage medium in the normal pressure medium tank 1 is considered to be fully hydrogenated until the tail gas flow rate is close to the flow rate of hydrogen entering the pressure reactor 4, and then the normal pressure medium tank 1 is replaced to carry out a new round of hydrogenation reaction; in addition, the incompletely reacted hydrogen in the pressure reactor 4 enters the tail gas recovery device 8 from the upper gas outlet for recovery and reuse.
The liquid in the normal pressure medium tank 1 after full hydrogenation is subjected to chromatographic analysis, and the result shows that the hydrogenation completion rate reaches 90%, and the circulating reaction system is considered to be capable of realizing effective continuous hydrogenation, so that the complexity of the hydrogenation reaction is reduced.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A circulation reaction system for liquid organic matter hydrogenation is characterized in that: the circulating reaction system comprises a normal pressure medium tank, a metering pump, a liquid flow controller, a pressure reactor, a gas flow controller, a hydrogen preheating device, a pressure reducing device and a tail gas recovery device;
the upper part of the normal pressure medium tank is provided with a liquid inlet, and the lower part of the normal pressure medium tank is provided with a liquid outlet;
the metering pump is a pump with a buffer device;
the pressure reactor is a reaction vessel containing a heating device, the upper part of the pressure reactor is provided with a liquid inlet and a gas outlet, and the lower part of the pressure reactor is provided with a gas inlet and a liquid outlet;
a liquid outlet of the normal pressure medium tank is connected with a liquid inlet of the pressure reactor, and a metering pump and a liquid flow controller are arranged on a pipeline which connects the liquid outlet of the normal pressure medium tank with the liquid inlet of the pressure reactor; the gas inlet of the pressure reactor is connected with an external hydrogen source, and a gas flow controller and a hydrogen preheating device are arranged on a pipeline connecting the gas inlet of the pressure reactor with the hydrogen source; the liquid outlet of the pressure reactor, the pressure reducing device and the liquid inlet of the normal pressure medium tank are sequentially connected; the tail gas recovery device is connected with a gas outlet of the pressure reactor.
2. The recycling reaction system for liquid organic matter hydrogenation according to claim 1, characterized in that: the heating device in the pressure reactor is an oil bath jacket or an electric heater, and the heating device is installed outside the reaction vessel.
3. The recycling reaction system for liquid organic matter hydrogenation according to claim 1, characterized in that: the tail gas recovery device comprises a condenser and a hydrogen storage tank; one end of the condenser is connected with a gas outlet of the pressure reactor, and the other end of the condenser is connected with the hydrogen storage tank.
4. The recycling reaction system for liquid organic matter hydrogenation according to claim 1, characterized in that: in the hydrogenation reaction process, the reaction temperature in the pressure reactor is 80-150 ℃, and the reaction pressure is 2 MP-6 MPa; correspondingly, an external hydrogen source is preheated to 80-150 ℃ by a hydrogen preheating device before entering the pressure reactor.
5. The recycling reaction system for liquid organic matter hydrogenation according to claim 1, characterized in that: the pressure reactor is internally provided with 5-20 catalytic bed layers.
6. The recycling reaction system for liquid organic matter hydrogenation according to claim 5, characterized in that: the height of the catalyst filled in each layer of the catalytic bed layer is 50 to 60 percent of the height of the catalytic bed layer.
7. The recycling reaction system for liquid organic matter hydrogenation according to claim 5, characterized in that: the pressure reactor is also internally provided with a gas distributor which is positioned below the catalytic bed layer.
8. A cyclic reaction system for the hydrogenation of liquid organics according to any of claims 1 to 7 wherein: the volume of the pressure reactor was 0.005m3～1.2m3(ii) a The flow rate of the hydrogen storage medium in the normal pressure medium tank entering the pressure reactor is 1L/min-100L/min, and the flow rate of the external hydrogen source entering the pressure reactor is 5L/min-50L/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254141A (en) * | 2022-08-30 | 2022-11-01 | 陕西氢易能源科技有限公司 | Micro-noble metal loaded catalyst, preparation method and application thereof |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254141A (en) * | 2022-08-30 | 2022-11-01 | 陕西氢易能源科技有限公司 | Micro-noble metal loaded catalyst, preparation method and application thereof |
| CN115254141B (en) * | 2022-08-30 | 2023-12-19 | 陕西氢易能源科技有限公司 | Micro-noble metal supported catalyst, preparation method and application thereof |
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