Online hydrogen content detection device and method for organic liquid hydrogen storage

Abstract

The invention discloses an organic liquid hydrogen storage online hydrogen content detection device and method. Comprising a detection box, a sealing cup is arranged in the detection box, a sample injection pipe is arranged on the detection box, a quantitative roller is arranged on the sample injection pipe, a plurality of quantitative grooves are formed in the quantitative roller, a temperature control assembly is arranged in the detection box, a weighing assembly is arranged below the sealing cup, a measuring pipe is arranged on the lower portion of the sealing cup, and a temperature control assembly is arranged on the measuring pipe. A refractometer is arranged in the detection box, and a transmission module is further arranged in the detection box. The method disclosed by the invention has the advantages that two groups of data are utilized to establish each stable standard curve at 25-30 DEG C, so that standard data can be checked at each temperature. And then the detection device is used for detecting the sample, the available hydrogen amount is obtained by comparing the standard curve at the corresponding temperature according to the detection temperature, the process of mutual correction at different temperatures is omitted, and errors generated in the process are erased, so that the detection data is more accurate.

Description

Technical Field

[0001] The present invention relates to the technical field of organic liquid hydrogen storage, and in particular to an online hydrogen content detection device and method for organic liquid hydrogen storage. Background Art

[0002] The principle of liquid organic hydrogen storage technology (LOHC for short) is to achieve hydrogen storage (chemical bonding) through the reversible reaction and hydrogenation reaction of unsaturated liquid organic matter such as certain olefins, alkynes or aromatic hydrocarbons and hydrogen, and to release hydrogen through dehydrogenation reaction. The mass hydrogen storage density is 5%-10%, and the hydrogen storage capacity is large. The hydrogen storage material is liquid organic matter, which can be transported at room temperature and pressure, which is convenient and safe.

[0003] The actual amount of hydrogen available in organic liquid hydrogen storage materials is not the theoretical amount of hydrogen storage. During the hydrogenation and dehydrogenation reactions of the test or production of organic liquid hydrogen storage materials, the focus will be on monitoring the changes in the available hydrogen storage capacity of the material, and continuous monitoring is also required to determine the completion of the hydrogenation or dehydrogenation reaction of the material. In the application scenarios of the recycling of organic liquid hydrogen storage materials and refueling in hydrogen refueling stations, the available hydrogen capacity of liquid hydrogen storage materials is also an important economic evaluation indicator.

[0004] The existing method for detecting the hydrogen storage density of organic liquid hydrogen storage materials is the group standard T / CAB10382020 "Drainage Method for Measuring the Hydrogen Storage Density of Hydrogenated Liquid Organic Hydrogen Storage Carriers". This method needs to be carried out in a certain dehydrogenation reaction device and under certain reaction conditions. The principle is to collect the hydrogen released by the organic liquid material through catalytic dehydrogenation by drainage, and after measurement, convert it into the ratio of the mass of hydrogen to the mass of the organic liquid hydrogen storage material as the available hydrogen storage capacity; however, this method requires sampling for offline testing in the laboratory, and the single detection time is long, the operation is complicated and cumbersome, and continuous online monitoring is not possible. It cannot be popularized and applied in continuous production and testing processes, as well as in the application scenarios of filling stations.

[0005] For example, an online monitoring method for the available hydrogen amount of an organic liquid hydrogen storage material with the publication number CN113588881A detects multiple sets of data on the relationship between the temperature, density, refractive index and available hydrogen amount of the hydrogen storage organic liquid, corrects the density and refractive index at the detection temperature of the organic liquid to the density and refractive index at the standard temperature, and summarizes the relationship between the refractive index, density and available hydrogen amount. When the available hydrogen amount in the organic liquid is detected online, the temperature, density and refractive index of the organic liquid are detected, and then the available hydrogen amount in the organic liquid is obtained according to the relationship, so as to realize the online monitoring of the available hydrogen amount of the hydrogen storage material. However, according to the data published in the invention application (shown in the appendix 1, 12 sets of real-time monitoring and measurement results and GC-MS method measurement of available hydrogen amount comparison), there is a certain error between the available hydrogen amount obtained by this method and the available hydrogen amount content of the sample measured by GC-MS method, especially when the hydrogen amount is low, the data error will be greater. Summary of the invention

[0006] 1. Technical issues to be solved

[0007] In view of the shortcomings of the prior art, the present invention provides an online hydrogen content detection device and method for organic liquid hydrogen storage, which has the advantages of obtaining the available hydrogen amount by comparing the detection temperature with the standard curve at the corresponding temperature, and transmitting the detection data to a detection center by using a transmission module, thereby realizing online detection of the available hydrogen amount in the organic liquid, and the detection data is more accurate.

[0008] (II) Technical solution

[0009] To achieve the above-mentioned purpose, the present invention provides the following technical solutions: an online hydrogen content detection device for organic liquid hydrogen storage, comprising a detection box, a sealing cup is arranged in the detection box, a sampling tube is arranged on the detection box, a quantitative roller is arranged on the sampling tube, a plurality of quantitative grooves are opened on the quantitative roller, a temperature control component is arranged in the detection box, a weighing component is arranged below the sealing cup, a measuring tube is arranged at the lower part of the sealing cup, a refractometer is arranged in the detection box, and a transmission module is also arranged in the detection box.

[0010] Preferably, a sample discharge tube is provided at the bottom of the sealing cup and a control valve is provided on the sample discharge tube.

[0011] Preferably, the bottom end of the sample feeding tube extends into the sealing cup, and a load-bearing block is provided at the bottom of the metering roller.

[0012] The above technical solution is adopted: the detection box provides an installation platform for each detection component, and the sealing cup is used to accommodate the sample to be detected. It adopts a sealed form to slow down the heat dissipation in the sealing cup as much as possible. The sample discharge tube arranged at the bottom of the sealing cup is used to discharge the sample in the sealing cup. A flange can be arranged at the end of the sample discharge tube to connect with the external recovery pipeline to avoid sample waste. The sampling tube is connected to the external organic liquid hydrogen storage device to provide the detection device with the detection sample. The quantitative roller is driven by a motor, and the volume of the sample entering the sealing cup can be controlled by controlling the rotation of the motor. The load-bearing block arranged at the bottom of the quantitative roller transfers the weight of the quantitative roller to the detection box to prevent the weight of the quantitative roller from affecting the weighing component to weigh the sealing cup.

[0013] Preferably, the temperature control structure of the temperature control component is arranged inside the sealing cup, and a temperature sensor is arranged inside the sealing cup.

[0014] Preferably, the end of the measuring tube is arranged above the sample inlet slot of the refractometer.

[0015] The above technical solution is adopted: the temperature control component is used to control the temperature of the sample in the sealed cup. The temperature control component cooperates with the temperature sensor in the sealed cup to adjust the temperature of the sample in the sealed cup to the nearest temperature with a standard curve, so as to use the standard curve corresponding to the temperature to measure the available hydrogen amount of the sample. By using the temperature control component to directly adjust the sample to the nearest temperature with a standard curve, and then measuring the density and refractive index of the sample at this temperature, the error caused by temperature conversion can be avoided, thereby reducing the error of the final test result.

[0016] A method for detecting the online hydrogen content of organic liquid hydrogen storage comprises the following steps:

[0017] S1. Density and refractive index detection of different hydrogen-containing organic liquids at different temperatures;

[0018] S2. Using GC-MS method to detect the amount of hydrogen available in hydrogen-containing organic liquid at the corresponding temperature;

[0019] S3. Establishment of standard curves of organic liquid density, refractive index and available hydrogen content at different temperatures;

[0020] S4. Using an online detection device to detect the density and refractive index of the organic liquid at a specific temperature;

[0021] S5. Compare the standard curve of the corresponding temperature to obtain the amount of available hydrogen in the organic liquid.

[0022] Preferably, the detection temperatures required for step S1 are 25°C, 25.5°C, 26°C, 26.5°C, 27°C, 27.5°C, 28°C, 29°C, 29.5°C and 30°C.

[0023] Preferably, step S4 specifically includes:

[0024] (1) The sample is introduced into the sealed cup from the sample inlet tube. The metering roller controls the amount of the sample entering the sealed cup. The weighing component weighs the sample. The density of the sample is calculated from the weight and volume of the sample.

[0025] (2) Using the temperature control component to detect and maintain the sample temperature in the sealed cup, opening the control valve on the measuring tube, dripping the sample into the refractometer, and the refractometer detecting the refractive index of the sample;

[0026] (3) The transmission module transmits the detection data to the external detection center.

[0027] The above technical solution is adopted: in the early stage of the test, the density and refractive index of the sample at 25℃~30℃ are tested respectively, and then the GC-MS method is used to test the available hydrogen content of the sample at 25℃~30℃, and the two sets of data are used to establish the standard curve at each stable temperature of 25℃~30℃, so that standard data can be checked at each temperature. Then the sample is tested by the detection device, and the available hydrogen content is obtained according to the standard curve at the corresponding temperature according to the detection temperature, which saves the process of mutual correction at different temperatures, eliminates the error generated by the process, and makes the test data more accurate.

[0028] (III) Beneficial effects

[0029] Compared with the prior art, the present invention provides an online hydrogen content detection device and method for organic liquid hydrogen storage, which has the following beneficial effects:

[0030] The device and method for detecting the online hydrogen content of organic liquid hydrogen storage respectively detects the density and refractive index of the sample at 25°C to 30°C in the early stage of the detection, and then uses the GC-MS method to detect the available hydrogen content of the sample at 25°C to 30°C, and uses the two sets of data to establish the standard curves at each stable temperature of 25°C to 30°C, so that standard data can be checked at each temperature. The sample is then tested by using the detection device, and the available hydrogen content is obtained by comparing the detected temperature with the standard curve at the corresponding temperature, eliminating the process of mutual correction at different temperatures, erasing the errors generated by the process, and making the detection data more accurate. The detection data is transmitted to the detection center by using the transmission module, so as to realize the online detection of the available hydrogen content in the organic liquid, and the detection data is more accurate. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A comparison chart of the detection result of an existing detection method proposed in the background technology of the present invention and the result of measuring the amount of available hydrogen by GC-MS;

[0032] Figure 2This is a structural schematic diagram of an online hydrogen content detection device for organic liquid hydrogen storage proposed by the present invention;

[0033] Figure 3 This is a flow chart of an online hydrogen content detection method for organic liquid hydrogen storage proposed by the present invention.

[0034] In the figure: 1-detection box, 2-sealing cup, 3-injection tube, 4-quantitative roller, 5-quantitative slot, 6-temperature control component, 7-weighing component, 8-measurement tube, 9-refractometer, 10-transmission module. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] See also Figure 1-3 An online hydrogen content detection device for organic liquid hydrogen storage includes a detection box 1, a sealing cup 2 is arranged in the detection box 1, a sampling tube 3 is arranged on the detection box 1, a quantitative roller 4 is arranged on the sampling tube 3, a plurality of quantitative grooves 5 are opened on the quantitative roller 4, a temperature control component 6 is arranged in the detection box 1, a weighing component 7 is arranged below the sealing cup 2, a measuring tube 8 is arranged at the lower part of the sealing cup 2, a refractometer 9 is arranged in the detection box 1, and a transmission module 10 is also arranged in the detection box 1.

[0037] Embodiment 1: A sample row tube is provided at the bottom of the sealing cup 2 and a control valve is provided on the sample row tube. The bottom end of the sample injection tube 3 extends into the sealing cup 2, and a load-bearing block is provided at the bottom of the quantitative roller 4. The detection box 1 provides an installation platform for each detection component. The sealing cup 2 is used to accommodate the sample to be detected. It adopts a sealed form, which can slow down the heat dissipation in the sealing cup 2 as much as possible. The sample row tube provided at the bottom of the sealing cup 2 is used to discharge the sample in the sealing cup 2. A flange can be provided at the end of the sample row tube to connect with an external recovery pipeline to avoid sample waste. The sample injection tube 3 is connected to an external organic liquid hydrogen storage device to provide a test sample for the detection device. The quantitative roller 4 is driven by a motor, and the volume of the sample entering the sealing cup 2 can be controlled by controlling the rotation of the motor. The load-bearing block provided at the bottom of the quantitative roller 4 transfers the weight of the quantitative roller 4 to the detection box 1, so as to avoid the weight of the quantitative roller 4 affecting the weighing component 7 to weigh the sealing cup 2.

[0038] Embodiment 2: The temperature control structure of the temperature control component 6 is arranged inside the sealed cup 2, and a temperature sensor is arranged inside the sealed cup 2. The end of the measuring tube 8 is arranged above the sample inlet slot of the refractometer 9. The temperature control component 6 is used to control the temperature of the sample in the sealed cup 2. The temperature control component 6 cooperates with the temperature sensor in the sealed cup 2 to adjust the temperature of the sample in the sealed cup 2 to the nearest temperature with a standard curve, so as to use the standard curve of the corresponding temperature to measure the amount of available hydrogen in the sample. By using the temperature control component 6 to directly adjust the sample to the nearest temperature with a standard curve, and then measuring the density and refractive index of the sample at this temperature, the error caused by temperature conversion can be avoided, thereby reducing the error of the final detection result.

[0039] A method for detecting the online hydrogen content of organic liquid hydrogen storage comprises the following steps:

[0040] S1. Density and refractive index detection of different hydrogen-containing organic liquids at different temperatures;

[0041] S2. Using GC-MS method to detect the amount of hydrogen available in hydrogen-containing organic liquid at the corresponding temperature;

[0042] S3. Establishment of standard curves of organic liquid density, refractive index and available hydrogen content at different temperatures;

[0043] S4. Using an online detection device to detect the density and refractive index of the organic liquid at a specific temperature;

[0044] S5. Compare the standard curve of the corresponding temperature to obtain the amount of available hydrogen in the organic liquid.

[0045] Embodiment 3: The detection temperatures required in step S1 are 25°C, 25.5°C, 26°C, 26.5°C, 27°C, 27.5°C, 28°C, 29°C, 29.5°C and 30°C. Step S4 specifically includes:

[0046] (1) The sample is introduced into the sealing cup 2 from the sample inlet tube 3, the metering roller 4 controls the amount of the sample entering the sealing cup 2, the weighing assembly 7 weighs the weight of the sample, and the density of the sample is calculated from the weight and volume of the sample;

[0047] (2) Using the temperature control assembly 6 to detect and maintain the sample temperature in the sealed cup 2, opening the control valve on the measuring tube 8, and dripping the sample into the refractometer 9, the refractometer 9 detects the refractive index of the sample;

[0048] (3) The transmission module 10 transmits the detection data to an external detection center.

[0049] In summary, the online hydrogen content detection device and method for organic liquid hydrogen storage, in the early stage of detection, respectively detects the density and refractive index of the sample at 25℃~30℃, and then uses the GC-MS method to detect the available hydrogen content of the sample at 25℃~30℃, and uses the two sets of data to establish the standard curve at each stable temperature of 25℃~30℃, so that standard data can be checked at each temperature. Then use the detection device to detect the sample, and compare the standard curve at the corresponding temperature according to the detection temperature to obtain the available hydrogen content, eliminating the process of mutual correction at different temperatures, eliminating the errors generated by the process, and making the detection data more accurate.

[0050] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the statement "comprise one" do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0051] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An online hydrogen content detection device for organic liquid hydrogen storage, characterized in that: It comprises a detection box, wherein a sealing cup is arranged in the detection box, a sampling tube is arranged on the detection box, a quantitative roller is arranged on the sampling tube, a plurality of quantitative grooves are opened on the quantitative roller, a temperature control component is arranged in the detection box, a weighing component is arranged below the sealing cup, a measuring tube is arranged at the lower part of the sealing cup, a refractometer is arranged in the detection box, and a transmission module is also arranged in the detection box.

2. The on-line hydrogen content detection device for organic liquid hydrogen storage according to claim 1 is characterized in that: A sample discharge tube is arranged at the bottom of the sealing cup and a control valve is arranged on the sample discharge tube.

3. An online hydrogen content detection device for organic liquid hydrogen storage according to claim 2, characterized in that: The bottom end of the sample injection tube extends into the sealing cup, and a load-bearing block is arranged at the bottom of the quantitative roller.

4. The on-line hydrogen content detection device for organic liquid hydrogen storage according to claim 3 is characterized in that: The temperature control structure of the temperature control component is arranged in the sealing cup, and a temperature sensor is arranged in the sealing cup.

5. The on-line hydrogen content detection device for organic liquid hydrogen storage according to claim 4 is characterized in that: The end of the measuring tube is arranged above the sample injection slot of the refractometer.

6. A method for detecting the online hydrogen content of organic liquid hydrogen storage using the online hydrogen content detection device for organic liquid hydrogen storage according to any one of claims 1 to 5, characterized in that: The steps include: S1. Density and refractive index detection of different hydrogen-containing organic liquids at different temperatures; S2. Using GC-MS method to detect the amount of hydrogen available in hydrogen-containing organic liquid at the corresponding temperature; S3. Establishment of standard curves of organic liquid density, refractive index and available hydrogen content at different temperatures; S4. Using an online detection device to detect the density and refractive index of the organic liquid at a specific temperature; S5. Compare the standard curve of the corresponding temperature to obtain the amount of available hydrogen in the organic liquid.

7. The method for detecting the online hydrogen content of an organic liquid hydrogen storage according to claim 6, characterized in that: The detection temperatures required for step S1 are 25°C, 25.5°C, 26°C, 26.5°C, 27°C, 27.5°C, 28°C, 29°C, 29.5°C and 30°C.

8. The method for detecting the online hydrogen content of organic liquid hydrogen storage according to claim 7, characterized in that: Step S4 specifically includes: The sample is introduced into the sealing cup from the sample inlet tube, the quantitative roller controls the amount of the sample entering the sealing cup, the weighing component weighs the weight of the sample, and the density of the sample is calculated from the weight and volume of the sample; The temperature of the sample in the sealed cup is adjusted to the nearest temperature with a standard curve by using the temperature control component in conjunction with the temperature sensor in the sealed cup, the control valve on the measuring tube is opened, the sample is dripped into the refractometer, and the refractometer detects the refractive index of the sample; The transmission module transmits the detection data to the external detection center.

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