Integrated apparatus for liquid organic hydrogen storage material dehydrogenation testing

Abstract

The utility model discloses a kind of integrated devices for liquid organic hydrogen storage material adds dehydrogenation test, belong to laboratory instrument field, including the reaction kettle of sealing cover, first pipeline and second pipeline downwards through sealing cover into the reaction kettle, the part above sealing cover of first pipeline is connected with inlet valve, the lower end of second pipeline is higher than the test liquid level in reaction kettle, the part above sealing cover of second pipeline is sequentially connected with condenser, pressure sensor, exhaust main switch and flowmeter according to the order of fluid leaving reaction kettle. The device can be used for hydrogenation test, and can also be used for dehydrogenation test, when the stability test of the same material is carried out in multiple cycles, it can be continuously carried out in the same device, it is more convenient, it can improve test efficiency, without repeatedly transferring the material to be tested, it can reduce the loss of material to be tested, it is beneficial to accurately test hydrogenation amount and dehydrogenation amount.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of integrated devices for liquid organic hydrogen storage material hydrogenation and dehydrogenation test, belong to laboratory instrument field. BACKGROUND

[0002] Liquid organic hydrogen carriers (LOHC) technology has the advantages of high volume hydrogen storage density, safe and efficient hydrogen storage process, and has good development prospects.

[0003] In the prior art, laboratory researchers usually use two separate intermittent devices for hydrogenation test and dehydrogenation test of liquid organic hydrogen storage materials, among which hydrogenation test is usually completed by high-temperature and high-pressure stainless steel reaction kettle, and dehydrogenation test is usually completed by self-made glass dehydrogenation device with condensation reflux component. Although different devices are used for hydrogenation test and dehydrogenation test, they can meet the basic needs of single test, but there are the following problems when testing the stability of the same material in multiple cycles:

[0004] When testing the stability of the same material in multiple cycles, frequent sampling and sampling are required in different devices, which increases the complexity of operation and reduces the test efficiency. Moreover, when the same sample is transferred between different devices, due to the problem of liquid droplet adhesion, it is easy to cause incomplete collection of reaction liquid, resulting in loss of target material and difficulty in accurately calculating parameters. UTILITY MODEL CONTENT

[0005] In order to overcome the shortcomings of the prior art, the utility model provides an integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material, which can complete hydrogenation test and dehydrogenation test of liquid organic hydrogen storage material with only one set of device.

[0006] The technical solution adopted by the utility model to solve its technical problems is:

[0007] An integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material, comprising a reaction kettle with a sealing cover, a first pipeline and a second pipeline passing through the sealing cover downward into the reaction kettle, the part of the first pipeline above the sealing cover is connected with an air inlet valve, the lower end of the second pipeline is higher than the test liquid level in the reaction kettle, and the part of the second pipeline above the sealing cover is connected with a condenser, a pressure sensor, an exhaust switch and a flow meter in turn according to the order of fluid leaving the reaction kettle.

[0008] The integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material can be used for hydrogenation test and dehydrogenation test. In the hydrogenation test, the first pipeline is used for gas inlet, and then the device is sealed. The hydrogenation amount of the liquid organic hydrogen storage material is obtained by the pressure change of the pressure sensor. In the dehydrogenation test, the gas in the reaction kettle is discharged through the exhaust switch, and the dehydrogenation amount is detected by the flow meter. In the device, the condenser is used to cool the volatile material back to the reaction system in the heating environment of the hydrogenation reaction and the dehydrogenation reaction. The pressure sensor is arranged before the exhaust switch and can work in the closed pipeline. The pressure sensor is arranged after the condenser, which reduces the influence of liquid drops on the accuracy of the pressure sensor. The flow meter is arranged after the exhaust switch, which avoids the influence of pressure change on the flow statistics during the reaction process.

[0009] Further, the integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material further comprises a temperature sensor, which penetrates downward through the sealing cover. The probe of the temperature sensor is located in the reaction kettle and below the test liquid level.

[0010] Further, the integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material further comprises a temperature sensor, which penetrates downward through the sealing cover. The probe of the temperature sensor is located in the reaction kettle and below the test liquid level.

[0011] Further, the integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material further comprises a mechanical stirring rod penetrating downward through the sealing cover. The lower end of the mechanical stirring rod is connected with a stirring paddle.

[0012] Further, the integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material further comprises a mechanical stirring rod penetrating downward through the sealing cover. The lower end of the mechanical stirring rod is connected with a stirring paddle.

[0013] Further, the lower end of the first pipeline is located below the test liquid level.

[0014] In this way, the sample can be taken through the first pipeline, and the hydrogenation amount can be detected after the hydrogenation reaction, which is verified with the result of the pressure sensor. Or the dehydrogenation amount can be detected after the dehydrogenation reaction, which is verified with the result of the flow meter.

[0015] Further, the part of the first pipeline above the sealing cover is divided into a sampling branch and an air inlet branch. The air inlet valve is connected to the air inlet branch. The sampling valve is connected to the sampling branch.

[0016] Further, the air inlet branch is divided into a hydrogen pipeline and a nitrogen pipeline in sequence according to the air inlet. The hydrogen on-off valve is connected to the hydrogen pipeline. The nitrogen on-off valve is connected to the nitrogen pipeline.

[0017] Further, the second pipeline is divided into a negative pressure branch and a metering branch after the exhaust main switch in sequence of fluid leaving the reactor, a metering switch valve is connected on the metering branch, the flow meter is arranged after the metering switch valve in sequence of fluid leaving the reactor, and the negative pressure branch is connected to a vacuum pump, and a negative pressure switch valve is arranged on the negative pressure branch.

[0018] Further, the second pipeline is divided into a negative pressure branch and a metering branch after the exhaust main switch in sequence of fluid leaving the reactor, a metering switch valve is connected on the metering branch, the flow meter is arranged after the metering switch valve in sequence of fluid leaving the reactor, and the negative pressure branch is connected to a vacuum pump, and a negative pressure switch valve is arranged on the negative pressure branch.

[0019] The integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material can be used for hydrogenation test and dehydrogenation test, and can continuously perform stability test on the same material in the same device, is more convenient, can improve test efficiency, does not need to repeatedly transfer the material to be tested, can reduce material loss, is beneficial to accurate test of hydrogenation amount and dehydrogenation amount.

[0020] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the present application. The objects and other advantages of the present application will be realized and attained by the structure particularly pointed out in the written description and claims hereof. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a structural schematic diagram of an integrated device for hydrogenation and dehydrogenation test of liquid organic hydrogen storage material provided by the embodiment of the present application.

[0022] Fig. 11 is a sealing cover; 110 is a reactor; 120 is a mechanical stirring rod; 121 is a stirring paddle; 122 is a motor; 210 is a temperature sensor; 220 is a pressure sensor; 31 is an air inlet branch; 310 is an air inlet valve; 311 is a hydrogen on-off valve; 312 is a nitrogen on-off valve; 32 is a second pipeline; 320 is an exhaust main switch; 321 is a pressure relief valve; 322 is a negative pressure switch valve; 323 is a metering switch valve; 324 is a flow meter; 35 is a first pipeline; 351 is a sampling branch; 410 is a condenser; 510 is a sampling valve. DETAILED DESCRIPTION

[0023] The embodiments of the present application will be described in detail below, examples of which are shown in the drawings, wherein the same or similar notations represent the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by reference to the drawings are exemplary only, and are merely intended to explain the present application, and should not be understood as limiting the present application.

[0024] The disclosure hereafter provides many different embodiments or examples for implementing different structures of the present application. For the purpose of simplifying the disclosure of the present application, the components and settings of specific examples are described hereafter. Of course, they are only examples, and the purpose is not to limit the present application. In addition, the present application can repeatedly refer to numbers and / or letters in different examples, and such repetition is for the purpose of simplification and clarity, which itself does not indicate the relationship between the various embodiments and / or settings discussed.

[0025] For the purpose of description, "front" and "back" used to describe the connection position are based on the sequence of fluid flow, the position where fluid arrives first is "front", and the position where fluid arrives later is "back".

[0026] The dehydrogenation reaction requires a higher temperature than the hydrogenation reaction, and the pressure requirement is much lower than the hydrogenation reaction. The hydrogenation reaction needs to be carried out in a closed space; the dehydrogenation reaction needs to be carried out in an open system, so as to discharge hydrogen in time. These characteristics make it difficult for existing autoclaves or glass devices to simultaneously meet the temperature and pressure conditions of the hydrogenation reaction and the temperature and pressure conditions of the dehydrogenation reaction. In particular, glass instruments cannot withstand the 5 MPa~10 MPa pressure required for hydrogenation; the pressure sensor in the autoclave is easy to be damaged by the high-temperature hydrogen storage liquid volatiles.

[0027] In view of the above problems, with reference to Figure 1 The embodiment of the present application provides an integrated device for testing liquid organic hydrogen storage material and dehydrogenation, which comprises a reaction kettle 110 with a sealing cover 11, a first pipeline 35 and a second pipeline 32 downwardly penetrating the sealing cover 11 into the reaction kettle 110, the part of the first pipeline 35 above the sealing cover 11 is connected with an air inlet valve 310, the lower end of the second pipeline 32 is higher than the test liquid level in the reaction kettle 110, and the part of the second pipeline 32 above the sealing cover 11 is sequentially connected with a condenser 410, a pressure sensor 220, an exhaust master switch 320 and a flow meter 324 in the order of fluid leaving the reaction kettle 110.

[0028] Before the experiment, the sealing cover 11 can be opened, and the liquid organic hydrogen storage material to be tested is added into the reactor 110, and then the sealing cover 11 is closed. When the hydrogenation reaction is carried out, the exhaust main switch 320 is closed, and the inlet valve 310 is opened to input the reaction gas. The hydrogenation amount can be calculated according to the result of the pressure sensor 220. When the dehydrogenation reaction is carried out, the inlet valve 310 is closed, and the exhaust main switch 320 is opened. The dehydrogenation amount can be calculated according to the result of the flow meter 324.

[0029] In the device, the reactor 110 and the sealing cover 11 can be made of stainless steel, Hastelloy, etc. The condenser 410 is used to recool the volatile material into the reaction system in the heating environment of the hydrogenation reaction and the dehydrogenation reaction. The pressure sensor 220 is arranged after the condenser 410 and before the exhaust main switch 320, so that the pressure sensor 220 can work in a closed pipeline, and the influence of the condensate drops or high-temperature volatile gas on the accuracy of the pressure sensor 220 is reduced. The flow meter 324 is arranged after the exhaust main switch 320, so as to avoid the influence of the pressure change in the reaction process on the flow statistics. The condenser 410 can also avoid the loss of material volatilization and ensure the purity of the collected hydrogen in the dehydrogenation process.

[0030] The hydrogenation reaction and the dehydrogenation reaction of the liquid organic hydrogen storage material both need to be heated to a certain temperature. If two devices are used alternately, each device needs to be reheated in each test, and the waste heat of the last test cannot be utilized, which causes waste of heat. After the test device of the embodiment of the application is used, the hydrogenation reaction and the dehydrogenation reaction are both carried out in the same device, the waste heat of the last test can be utilized, and the test energy consumption is reduced.

[0031] The temperature of the reactor 110 can be controlled by oil bath heating. Preferably, the integrated device for testing the hydrogenation and dehydrogenation of the liquid organic hydrogen storage material further comprises a temperature sensor 210. The temperature sensor 210 penetrates downward through the sealing cover 11, and the probe of the temperature sensor 210 is located in the reactor 110 and below the test liquid level. After the temperature sensor 210 is used for monitoring, electromagnetic heating, electric heating wire heating, etc. can also be used.

[0032] In some embodiments, the integrated device for testing the hydrogenation and dehydrogenation of the liquid organic hydrogen storage material further comprises a controller (not shown in the figure), which is in signal connection with the pressure sensor 220, the temperature sensor 210 and the flow meter 324. Specifically, the pressure sensor 220, the temperature sensor 210 and the flow meter 324 are connected with a computer, and the change curve can be recorded in real time.

[0033] To improve the reaction efficiency, preferably, the integrated device for liquid organic hydrogen storage material dehydrogenation test further comprises a mechanical stirring rod 120 downwardly penetrating through the sealing cover 11, and a stirring paddle 121 is connected to the lower end of the mechanical stirring rod 120. Specifically, an electric motor 122 is connected to the upper end of the mechanical stirring rod 120.

[0034] In some embodiments, the lower end of the first pipeline 35 is below the test liquid level. In this way, the first pipeline 35 can be used for sampling. Preferably, the portion of the first pipeline 35 above the sealing cover 11 branches into a sampling branch 351 and a gas inlet branch 31, and a sampling valve 510 is connected to the sampling branch 351, and a gas inlet valve 310 is connected to the gas inlet branch 31. Specifically, the gas inlet branch 31 further branches into a hydrogen pipeline and a nitrogen pipeline in sequence of gas inlet, and a hydrogen on-off valve 311 is connected to the hydrogen pipeline, and a nitrogen on-off valve 312 is connected to the nitrogen pipeline.

[0035] Preferably, the sampling valve 510 is a precision valve, and the single sampling volume is in the order of microliters to avoid excessive sampling and pressure relief problems.

[0036] In this embodiment, before the experiment, the sealing cover 11 can be opened, the liquid organic hydrogen storage material to be tested is added to the reaction kettle 110, and then the sealing cover 11 is closed. During the hydrogenation reaction, the exhaust main switch 320 is closed, the hydrogen on-off valve 311 is opened to introduce hydrogen, the gas inlet valve 310 is opened to input gas, and the hydrogenation amount can be calculated according to the result of the pressure sensor 220. The sampling valve 510 can also be opened during the reaction to suck a small amount of the test material to detect the hydrogen absorption amount. During the dehydrogenation reaction, the sampling valve 510, the gas inlet valve 310, the hydrogen on-off valve 311, and the nitrogen on-off valve 312 are closed, and the exhaust main switch 320 is opened. The dehydrogenation amount can be calculated according to the result of the flow meter 324, and the sampling valve 510 can also be opened during the reaction to suck a small amount of the test material to detect the dehydrogenation amount. That is, there are two methods for each of the hydrogenation reaction and the dehydrogenation reaction to verify the results.

[0037] In some embodiments, the second pipeline 32 is divided into a negative pressure branch and a metering branch after the exhaust main switch 320 in the order of fluid leaving the reactor 110 above the sealing cover 11, the metering switch valve 323 is connected on the metering branch, the flow meter 324 is arranged after the metering switch valve 323 in the order of fluid leaving the reactor 110, the end of the negative pressure branch is connected to a vacuum pump (not shown in the figure), and the negative pressure switch valve 322 is arranged on the negative pressure branch. The flow meter 324 is arranged on a separate branch, and when the reactor 110 is ventilated, the metering branch is not passed through, so that the change of the resulting curve formed by the flow meter 324 is not caused, and the experimental results are facilitated. Preferably, the second pipeline 32 is further divided into a pressure relief branch after the exhaust main switch 320 in the order of fluid leaving the reactor 110 above the sealing cover 11, the pressure relief branch is connected with the negative pressure branch and the metering branch in parallel, and the pressure relief valve 321 is connected on the pressure relief branch. On the metering branch, the flow meter 324 can be further connected to a drainage device (not shown in the figure).

[0038] In combination with the above preferred embodiments, the complete experimental process is as follows:

[0039] Before the experiment, the sealing cover 11 can be opened, and the liquid organic hydrogen storage material to be tested is added into the reactor 110, and then the sealing cover 11 is closed.

[0040] In the hydrogenation test, the negative pressure switch valve 322 is opened, and the remaining valves are closed, vacuum is drawn through the negative pressure branch, the nitrogen on-off valve 312 and the inlet valve 310 are opened to introduce nitrogen, the above vacuum-drawing-nitrogen-introducing process is repeated three times, then vacuum is drawn, heating and stirring are started. After reaching the preset temperature, the hydrogen on-off valve 311 and the inlet valve 310 are opened to introduce hydrogen gas at a preset pressure, all valves are closed to form a closed system, and hydrogenation is completed. The real-time hydrogenation amount can be calculated by using the hydrogen consumption amount or the proportion of hydrogenated products, the former is calculated by detecting the pressure change through the pressure sensor 220, and the latter is calculated by sampling detection through the sampling branch 351.

[0041] In the dehydrogenation test, the liquid organic hydrogen storage material previously hydrogenated is not taken out, the atmosphere is connected through the pressure relief valve 321, the remaining high-pressure hydrogen gas in the reaction is discharged in advance, then the negative pressure switch valve 322 is opened to draw vacuum, and all valves are closed after completion. Stirring is maintained, the metering switch valve 323 is opened after reaching the preset temperature, and the dehydrogenation test is completed. The real-time dehydrogenation amount can be calculated by using the hydrogen release amount or the proportion of dehydrogenated products, the former is detected by the hydrogen generation amount through the flow meter 324 or the drainage amount of the drainage device, and the latter is calculated by sampling detection through the sampling valve 510.

[0042] The stability test of multiple cycles of the same material can be continuously carried out in the same device, which is more convenient, can improve the test efficiency, and provides two methods of hydrogen end and liquid organic hydrogen storage material end for calculating the hydrogenation amount and dehydrogenation amount, which can verify each other and improve the accuracy.

[0043] In the description of the present specification, the description referring to the terms "one embodiment", "certain embodiments", "illustrative embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0044] The above is the preferred embodiment of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which are also considered within the protection scope of the present application.

Claims

1. An integrated device for testing the addition and dehydrogenation of liquid organic hydrogen storage materials, comprising a reaction vessel (110) with a sealed cap (11), characterized in that, It also includes a first pipe (35) and a second pipe (32) that pass downward through the sealing cover (11) into the reactor (110). The first pipe (35) is connected to an air inlet valve (310) above the sealing cover (11). The lower end of the second pipe (32) is higher than the test liquid level in the reactor (110). The second pipe (32) is connected to a condenser (410), a pressure sensor (220), an exhaust main switch (320), and a flow meter (324) in sequence above the sealing cover (11) in the order in which the fluid leaves the reactor (110).

2. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 1, characterized in that, It also includes a temperature sensor (210) that extends downward through the sealing cap (11) and whose probe is located inside the reactor (110) and below the test liquid level.

3. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 2, characterized in that, It also includes a controller that is signal-connected to the pressure sensor (220), the temperature sensor (210), and the flow meter (324).

4. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 1, characterized in that, It also includes a mechanical stirring rod (120) that extends downward through the sealing cap (11), the lower end of which is connected to a stirring paddle (121).

5. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 4, characterized in that, The upper end of the mechanical stirring rod (120) is connected to a motor (122).

6. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 1, characterized in that, The lower end of the first pipeline (35) is below the test liquid level.

7. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 6, characterized in that, The first pipeline (35) branches into a sampling branch (351) and an air intake branch (31) above the sealing cap (11). The air intake valve (310) is connected to the air intake branch (31), and a sampling valve (510) is connected to the sampling branch (351).

8. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 7, characterized in that, The intake branch (31) is further divided into a hydrogen pipeline and a nitrogen pipeline before the intake valve (310) according to the intake sequence. A hydrogen on / off valve (311) is connected to the hydrogen pipeline, and a nitrogen on / off valve (312) is connected to the nitrogen pipeline.

9. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 1, characterized in that, The second pipeline (32) above the sealing cap (11) is divided into a negative pressure branch and a metering branch after the main exhaust switch (320) according to the order in which the fluid leaves the reactor (110). A metering switch valve (323) is connected to the metering branch. The flow meter (324) is set after the metering switch valve (323) according to the order in which the fluid leaves the reactor (110). The end of the negative pressure branch is connected to a vacuum pump. A negative pressure switch valve (322) is provided on the negative pressure branch.

10. The integrated device for testing the addition and removal of hydrogen from liquid organic hydrogen storage materials according to claim 9, characterized in that, The second pipeline (32) above the sealing cover (11) branches off into a pressure relief branch after the main exhaust switch (320) in the order in which the fluid leaves the reactor (110). The pressure relief branch is connected in parallel with the negative pressure branch and the metering branch. A pressure relief valve (321) is connected to the pressure relief branch.

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