CN113588881A - On-line monitoring method for available hydrogen amount of organic liquid hydrogen storage material - Google Patents
On-line monitoring method for available hydrogen amount of organic liquid hydrogen storage material Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000001257 hydrogen Substances 0.000 title claims abstract description 185
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 185
- 239000007788 liquid Substances 0.000 title claims abstract description 112
- 239000011232 storage material Substances 0.000 title claims abstract description 73
- 238000012544 monitoring process Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000012806 monitoring device Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000012937 correction Methods 0.000 claims description 2
- 238000001739 density measurement Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 18
- 238000004364 calculation method Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XIVQMBJJCVVPCF-UHFFFAOYSA-N methylcyclohexane;toluene Chemical compound CC1CCCCC1.CC1=CC=CC=C1 XIVQMBJJCVVPCF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 unsaturated aromatic organic compounds Chemical class 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses an on-line monitoring method of available hydrogen amount of an organic liquid hydrogen storage material, which comprises the following steps: s1, temperature t of samplexRefractive index nxAnd density ρxS2, detecting the available hydrogen amount of the organic liquid, S3, the available hydrogen amount and the refractive index nxAnd density ρxEstablishing a standard curve, and monitoring the available hydrogen amount of the unknown organic liquid hydrogen storage material on line by S4; the invention establishes the online real-time monitoring method of the available hydrogen amount of the organic liquid hydrogen storage material for the first time, the method has simple and convenient operation and low cost, can be directly arranged on pipelines of hydrogenation and dehydrogenation tests and production devices of the organic liquid hydrogen storage material, and can also be arranged in a conveying pipeline of a filling station, thereby realizing the online monitoring of the available hydrogen amount of the hydrogen storage material; the method can be popularized and applied to the monitoring scene of the available hydrogen amount of various hydrogen storage materials; the online real-time monitoring method is suitable for large-batch and continuous monitoring, and is rapid and wide in applicability.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage, and particularly relates to an online monitoring method for the amount of available hydrogen of an organic liquid hydrogen storage material.
Background
Hydrogen is a clean energy with high efficiency, and the storage and transportation of hydrogen are key problems affecting the large-scale application of hydrogen energy. Common hydrogen storage methods include high-pressure gaseous hydrogen storage, liquid hydrogen storage, metal hydrogen storage, organic liquid hydride hydrogen storage, and the like. Organic liquid hydrogen storage is the immobilization of hydrogen to hydrocarbons, alkynes, and certain unsaturated aromatic organic compounds by hydrogenation reactions and the formation of stable hydrogenated organic compound liquids, such as benzene-cyclohexane, methyl benzene-methylcyclohexane, and the like. When the hydrogen-loaded organic liquid compound reaches a user end, hydrogen is released through a catalytic reaction, the dehydrogenated organic liquid can further continue to carry out a hydrogenation reaction to store hydrogen, and the hydrogen is released through dehydrogenation again for recycling. The organic liquid hydrogen storage material has higher hydrogen storage quality and volume hydrogen storage density, is in a liquid state at normal temperature and normal pressure, can be stored and transported at normal temperature and normal pressure like gasoline and diesel oil, and can ensure that the storage and transportation process is safe and efficient and the cost of hydrogen energy scale utilization is greatly reduced by utilizing the existing transportation mode of gasoline and diesel oil and facilities of a gas station. The theoretical hydrogen storage qualities of the different organic liquid hydrogen storage materials are shown in table 1 below:
TABLE 1 theoretical hydrogen storage quality for different organic liquid hydrogen storage materials
The actual amount of hydrogen available for the organic liquid hydrogen storage material is not the theoretical amount of hydrogen stored. In the process of hydrogenation and dehydrogenation reaction for testing or producing the organic liquid hydrogen storage material, the change of the available hydrogen storage amount of the material is mainly monitored, and meanwhile, continuous monitoring is needed so as to judge the completion condition of the hydrogenation or dehydrogenation reaction of the material. In the application scenes of recycling the organic liquid hydrogen storage material and filling the organic liquid hydrogen storage material in a hydrogen station, the available hydrogen amount of the liquid hydrogen storage material is also an important economic evaluation index.
The existing detection method for the hydrogen storage density of the organic liquid hydrogen storage material is a drainage method for measuring the hydrogen storage density of a hydrogenated liquid organic hydrogen storage carrier, which is a group standard T/CAB 10382020, wherein the method needs to be carried out under a certain dehydrogenation reaction device and certain reaction conditions, and the principle is that hydrogen released by the organic liquid material through dehydrogenation of a catalyst is collected in a drainage mode and is converted into the available hydrogen storage amount according to the mass ratio of the hydrogen to the organic liquid hydrogen storage material after measurement; however, the method needs to perform off-line detection in a laboratory, has long single detection time, is complex and tedious to operate, cannot perform continuous on-line monitoring, and cannot be popularized and applied in the continuous production and test process and the application scene of a filling station; therefore, there is a need to develop a method for accurately and online monitoring the amount of hydrogen available in the organic liquid hydrogen storage material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an on-line monitoring method for the amount of hydrogen available in an organic liquid hydrogen storage material. The method solves the problems that the existing detection method needs to sample and detect in a laboratory off-line mode, is long in single detection time, complex and tedious in operation, cannot continuously monitor on line, cannot be popularized and applied in the continuous production and test process and the application scene of a filling station and the like.
In order to solve the problems in the prior art, the invention is realized by the following technical scheme:
an on-line monitoring method for the amount of hydrogen available for an organic liquid hydrogen storage material comprises the following steps:
s1, temperature t of samplexRefractive index nxAnd density ρxThe determination of (1): starting the infusion pump of the monitoring device, making the organic liquid in the organic liquid hydrogen storage material flow through the detector, reading and recording the temperature t measured by the detector in the on-line monitoring devicexValue, refractive index nxValue and density ρxCollecting the organic liquid flowing out from the detector while reading the value;
s2, detecting the amount of available hydrogen of the organic liquid: pretreating the organic liquid obtained in the step S1, and then analyzing by adopting GC-MS (gas chromatography-Mass spectrometer) to obtain the amount of available hydrogen in the organic liquid;
s3 usable hydrogen amount and refractive index nxAnd density ρxEstablishment of a standard curve: according to organic liquidsEstablishing a standard curve equation of the available hydrogen amount and the refractive index; establishing a standard curve equation of the available hydrogen amount and the density according to the available hydrogen amount of the organic liquid and the density at the standard temperature;
s4, online monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material: real-time reading of temperature t measured by detector in on-line monitoring devicexValue, refractive index nxValue and density ρxAnd obtaining the real-time available hydrogen amount of the organic liquid through the curve in the step S3, thereby realizing the online real-time monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material.
Further, step S1 includes the step of obtaining a refractive index n of the samplexAnd density ρxA step of performing correction at a standard temperature, specifically, selecting a standard temperature for the refractive index n obtained in step S1xValue and density ρxThe value is corrected, and in step S3, the amount of hydrogen and the corrected refractive index n are usedxAnd density ρxA standard curve is established.
Further, a conversion formula of refractive index at a standard temperature of 20 ℃: n is20＝nx+0.0003×(tx-20), wherein n20Is a refractive index at 20 ℃, nxIs at an ambient temperature txRefractive index at time, density ρ at 20 ℃ standard temperaturexThe conversion formula of (c): rho20＝ρx+0.000008×(tx-20), wherein ρ20Is a density at 20 ℃, pxIs at an ambient temperature txDensity of the particles.
Furthermore, the standard curve equation of the available hydrogen amount and the refractive index is W-57.524 n20 2-216.18n20+200.26，R20.9993, wherein 1.3100 is less than or equal to n20Less than or equal to 1.5570; the standard curve equation of the available hydrogen amount and the density is W-40.845 rho20+44.047，R20.9889, wherein n20> 1.5570 or n20＜1.310。
Further, in step S1, the detector includes an online thermometer, an online refractometer, and an online densitometer.
Further, the on-line refractometer has a refractive index measurement range of 1.310-1.557.
Further, the density measurement range of the on-line densitometer is 0.0000 to 2.0000g/cm3。
Further, in step S2, a specific method of pretreating the organic liquid is as follows: and (3) sucking the organic liquid into a volumetric flask, adding an organic solvent, carrying out vortex mixing, carrying out ultrasonic treatment for 5-10min, then carrying out constant volume, and filtering through a filter membrane of 0.22 mu m, wherein the organic solvent is one of acetone, N-dimethylformamide, N-hexane and acetonitrile.
Further, in step S2, the chromatographic conditions of the GC-MS are as follows: the gas chromatography instrument is an Agilent 7890B system, and the column temperature is as follows: starting at 60 ℃, increasing the temperature to 180 ℃ at 30 ℃/min, then increasing the temperature to 250 ℃ at 4 ℃/min, maintaining the temperature for 2.5min, and carrying gas: nitrogen, carrier gas flow rate: 0.8 mL/min; sample introduction amount: 0.3 mu L; the type of the chromatographic column: DB-17MS or DB-5MS, 30m × 0.25mm,0.25 μm or 60m × 0.25mm,0.25 μm; the mass spectral conditions of the GC-MS were as follows: the mass spectrometer is an Agilent 5977A system, and the mass spectrum ionization mode is as follows: an EI ion source; mass scan range: 40amu to 350 amu; the detection mode is as follows: transmission line: 280 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃; voltage: 70 ev.
Further, in step S2, the calculation formula of the amount of available hydrogen in the organic liquid is as follows:
wherein w represents the mass percentage of available hydrogen of the organic liquid hydrogen storage material; omega1-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material added with 2H in the mass spectrogram; omega2-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material added with 4H in the mass spectrogram; omega2n-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material plus n × 2H in the mass spectrogram; m2HGeneration ofTable initial molecular weight of the organic liquid hydrogen storage material plus 2H; m4H-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after 4H; m2nH-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after n x 2H.
According to the invention, the relationship between the refractive index and the density and the available hydrogen content of the organic liquid hydrogen storage material is found according to the difference between the refractive index and the density of different organic liquid hydrogen storage materials after hydrogenation or dehydrogenation, so as to determine the standard curve relationship of the available hydrogen content of the organic liquid hydrogen storage material and the refractive index and the density within a certain range, and the temperature t measured by a detector in an online monitoring device is read in real time on line according to the standard curve relationshipxValue, refractive index nxValue and density ρxAnd after the value is corrected, the real-time available hydrogen amount of the organic liquid is obtained, so that the online real-time monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material is realized.
Compared with the prior art, the invention has the following advantages:
1) the invention establishes the online real-time monitoring method of the available hydrogen amount of the organic liquid hydrogen storage material for the first time, the method has simple and convenient operation and low cost, can be directly arranged on pipelines of hydrogenation and dehydrogenation tests and production devices of the organic liquid hydrogen storage material, and can also be arranged in a conveying pipeline of a filling station, thereby realizing the online monitoring of the available hydrogen amount of the hydrogen storage material; the method can be popularized and applied to the monitoring scene of the available hydrogen amount of various hydrogen storage materials;
2) the online real-time monitoring method is suitable for large-scale and continuous monitoring, is quick and wide in applicability, and has the reliability of the monitoring result of more than 95 percent, so that the online real-time monitoring method has a certain application prospect in the aspect of monitoring the available hydrogen amount of the organic liquid hydrogen storage material.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of the on-line real-time monitoring method of the present invention;
FIG. 2 is a standard curve equation of the amount of hydrogen available and the refractive index at a standard temperature according to the present invention;
FIG. 3 is a standard curve equation of the amount of hydrogen available in the present invention versus the density at a standard temperature.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
The reagents and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
An on-line monitoring method for the amount of hydrogen available for an organic liquid hydrogen storage material comprises the following steps:
s1, temperature t of 20 samplesxRefractive index nxAnd density ρxThe determination of (1): when the hydrogenation or dehydrogenation reaction of the organic liquid hydrogen storage material is started, an online monitoring device is connected to a monitoring point, then an infusion pump of the monitoring device is started, the organic liquid flows through a detector, and the temperature t measured by the detector in the online monitoring device is read and recordedxValue, refractive index nxValue and density ρxThe detector comprises an online thermometer, an online refractometer and an online densitometer, wherein the online thermometer is used for recording the ambient temperature, the refractive index measuring range of the online refractometer (a commercially available online refractometer or an online refractometer) is 1.310-1.557, and the density measuring range of the online densitometer is 0.0000-2.0000g/cm3(ii) a While reading, 20 portions of the organic liquid flowing out of the detector were collected;
s2 refractive index of 20 samplesnxAnd density ρxCalibration at standard temperature: selecting a standard temperature of 20 ℃ for the refractive index n obtained in step S1xValue and density ρxThe values are corrected, and the conversion formula of the refractive index at the standard temperature is as follows: n is20＝nx+0.0003×(tx-20), wherein n20Is a refractive index at 20 ℃, nxIs at an ambient temperature txRefractive index at time, density at standard temperature ρxThe conversion formula of (c): rho20＝ρx+0.000008× (tx-20), wherein ρ20Is a density at 20 ℃, pxIs at an ambient temperature txDensity of time;
s3, detecting the available hydrogen amount of 20 samples of organic liquid: pretreating the organic liquid obtained in the step S1, wherein the specific method for pretreating the organic liquid is as follows: sucking 10-50 mu L of organic liquid into a 10mL volumetric flask, adding an organic solvent, carrying out vortex mixing, carrying out ultrasonic treatment for 5-10min, then carrying out constant volume, and filtering through a filter membrane of 0.22 mu m, wherein the organic solvent is one of acetone, N-dimethylformamide, N-hexane and acetonitrile; then, the analysis is carried out by GC-MS, and the chromatographic conditions of the GC-MS are as follows: the gas chromatography instrument is an Agilent 7890B system, and the column temperature is as follows: starting at 60 ℃, increasing the temperature to 180 ℃ at 30 ℃/min, then increasing the temperature to 250 ℃ at 4 ℃/min, maintaining the temperature for 2.5min, and carrying gas: nitrogen, carrier gas flow rate: 0.8 mL/min; sample introduction amount: 0.3 mu L; the type of the chromatographic column: DB-17MS or DB-5MS, 30m × 0.25mm,0.25 μm or 60m × 0.25mm,0.25 μm; the mass spectral conditions of the GC-MS were as follows: the mass spectrometer is an Agilent 5977A system, and the mass spectrum ionization mode is as follows: an EI ion source; mass scan range: 40amu to 350 amu; the detection mode is as follows: transmission line: 280 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃; voltage: 70 ev; obtaining the amount of available hydrogen in the organic liquid, wherein the calculation formula of the amount of available hydrogen in the organic liquid is as follows:
wherein w represents the mass percentage of the available hydrogen of the organic liquid hydrogen storage material；ω1-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material added with 2H in the mass spectrogram; omega2-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material added with 4H in the mass spectrogram; omega2n-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material plus n × 2H in the mass spectrogram; m2H-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after 2H; m4H-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after 4H; m2nH-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after n x 2H;
temperature t of the 20 samplesxRefractive index nxAnd density ρxAnd the corrected value thereof, the results of measuring the available hydrogen amount in the organic liquid by the 20 samples are shown in the table 2:
TABLE 220 temperatures t of the samplesxRefractive index nxDensity rhoxCorrected value and available hydrogen gas amount result thereof
S4, 20 samples available hydrogen amount and corrected refractive index nxAnd density ρxEstablishment of a standard curve: establishing a standard curve equation of the available hydrogen amount and the refractive index according to the available hydrogen amount of the organic liquid and the refractive index at the standard temperature; the standard curve equation is W-57.524 nx 2-216.18nx+200.26，R20.9993, wherein 1.3100 is less than or equal to nxLess than or equal to 1.5570; according to the available hydrogen amount of the organic liquid and the density at the standard temperature, a standard curve equation of the available hydrogen amount and the density is established, and the standard curve equation is that W is-40.845 rhox+44.047，R20.9889, wherein nx> 1.5570 or nx＜1.310；
S5, online monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material: real-time reading of temperature t measured by detector in on-line monitoring devicexValue, refractive index nxValue and density ρxAnd (4) after the value is corrected by the method in the step S2, obtaining the real-time available hydrogen amount of the organic liquid through the curve in the step S4, thereby realizing the online real-time monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material.
In the monitoring method, 12 groups of unknown samples are selected for real-time monitoring measurement, and simultaneously, the GC-MS method is used for determining the available hydrogen amount of the 12 groups of samples, so that the reliability of the real-time monitoring method is further verified, and the results are shown in Table 3:
TABLE 3 comparison of the results of the real-time monitoring measurement of the present invention and the measurement of the amount of hydrogen available by GC-MS method
As can be seen from the results in Table 3, the content of the available hydrogen of the sample measured by the real-time monitoring method is almost the same as that of the available hydrogen of the sample measured by the GC-MS method, which shows that the real-time monitoring result of the invention is reliable and the invention can be rapidly used for the online real-time monitoring of the available hydrogen of the unknown organic liquid hydrogen storage material.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein.
Claims (10)
1. An on-line monitoring method for the amount of hydrogen available for an organic liquid hydrogen storage material is characterized by comprising the following steps:
s1, temperature t of samplexRefractive index nxAnd density ρxThe determination of (1): starting the infusion pump of the monitoring device, making the organic liquid in the organic liquid hydrogen storage material flow through the detector, reading and recording the temperature t measured by the detector in the on-line monitoring devicexValue, refractive index nxValue and density ρxCollecting the organic liquid flowing out from the detector while reading the value;
s2, detecting the amount of available hydrogen of the organic liquid: pretreating the organic liquid obtained in the step S1, and then analyzing by adopting GC-MS (gas chromatography-Mass spectrometer) to obtain the amount of available hydrogen in the organic liquid;
s3 usable hydrogen amount and refractive index nxAnd density ρxEstablishment of a standard curve: establishing a standard curve equation of the available hydrogen amount and the refractive index according to the available hydrogen amount of the organic liquid and the refractive index at the standard temperature; establishing a standard curve equation of the available hydrogen amount and the density according to the available hydrogen amount of the organic liquid and the density at the standard temperature;
s4, online monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material: real-time reading of temperature t measured by detector in on-line monitoring devicexValue, refractive index nxValue and density ρxAnd obtaining the real-time available hydrogen amount of the organic liquid through the curve in the step S3, thereby realizing the online real-time monitoring of the available hydrogen amount of the unknown organic liquid hydrogen storage material.
2. The method of on-line monitoring the amount of hydrogen available from an organic liquid hydrogen storage material as claimed in claim 1, wherein step S1 further comprises obtaining a refractive index n of the samplexAnd density ρxA step of performing correction at a standard temperature, specifically, selecting a standard temperature for the refractive index n obtained in step S1xValue and density ρxThe value is corrected, and in step S3, the amount of hydrogen and the corrected refractive index n are usedxAnd density ρxA standard curve is established.
3. The method for on-line monitoring the amount of hydrogen available for organic liquid hydrogen storage material of claim 2, wherein the conversion formula of the refractive index at a standard temperature of 20 ℃ is: n is20＝nx+0.0003×(tx-20), wherein n20Is a refractive index at 20 ℃, nxIs at an ambient temperature txRefractive index at time, density ρ at 20 ℃ standard temperaturexThe conversion formula of (c): rho20＝ρx+0.000008×(tx-20), wherein ρ20Is a density at 20 ℃, pxIs at an ambient temperature txDensity of the particles.
4. The method for on-line monitoring the amount of available hydrogen in organic liquid hydrogen storage material as claimed in claim 3, wherein the standard curve equation of the amount of available hydrogen and the refractive index is W-57.524 n20 2-216.18n20+200.26，R20.9993, wherein 1.3100 is less than or equal to n20Less than or equal to 1.5570; the standard curve equation of the available hydrogen amount and the density is W-40.845 rho20+44.047，R20.9889, wherein n20> 1.5570 or n20＜1.310。
5. The method for on-line monitoring the amount of hydrogen available from an organic liquid hydrogen storage material of claim 1, wherein the detectors comprise an on-line thermometer, an on-line refractometer and an on-line densitometer in step S1.
6. The method for on-line monitoring of the amount of hydrogen available to an organic liquid hydrogen storage material of claim 5, wherein the on-line refractometer has a refractive index measurement range of 1.310-1.557.
7. The method for on-line monitoring of the amount of hydrogen available to an organic liquid hydrogen storage material of claim 5, wherein the on-line densitometer has a density measurement in the range of 0.0000 to 2.0000g/cm3。
8. The method for on-line monitoring the amount of hydrogen available for organic liquid hydrogen storage material according to claim 1, wherein in step S2, the specific method for pre-treating the organic liquid is as follows: and (3) sucking the organic liquid into a volumetric flask, adding an organic solvent, carrying out vortex mixing, carrying out ultrasonic treatment for 5-10min, then carrying out constant volume, and filtering through a filter membrane of 0.22 mu m, wherein the organic solvent is one of acetone, N-dimethylformamide, N-hexane and acetonitrile.
9. The method for on-line monitoring the amount of hydrogen available from an organic liquid hydrogen storage material according to claim 1, wherein in step S2, the chromatographic conditions of the GC-MS are as follows: the gas chromatography instrument is an Agilent 7890B system, and the column temperature is as follows: starting at 60 ℃, increasing the temperature to 180 ℃ at 30 ℃/min, then increasing the temperature to 250 ℃ at 4 ℃/min, maintaining the temperature for 2.5min, and carrying gas: nitrogen, carrier gas flow rate: 0.8 mL/min; sample introduction amount: 0.3 mu L; the type of the chromatographic column: DB-17MS or DB-5MS, 30m × 0.25mm,0.25 μm or 60m × 0.25mm,0.25 μm; the mass spectral conditions of the GC-MS were as follows: the mass spectrometer is an Agilent 5977A system, and the mass spectrum ionization mode is as follows: an EI ion source; mass scan range: 40amu to 350 amu; the detection mode is as follows: transmission line: 280 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃; voltage: 70 ev.
10. The method for on-line monitoring the amount of hydrogen available from an organic liquid hydrogen storage material as claimed in claim 1, wherein in step S2, the amount of hydrogen available in the organic liquid is calculated as follows:
wherein w represents the mass percentage of available hydrogen of the organic liquid hydrogen storage material; omega1-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material added with 2H in the mass spectrogram; omega2Represents the initial molecular weight of the organic liquid hydrogen storage material plus 4H in mass spectrumArea percentage occupied in the figure; omega2n-represents the area percentage of the initial molecular weight of the organic liquid hydrogen storage material plus n × 2H in the mass spectrogram; m2H-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after 2H; m4H-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after 4H; m2nH-represents the initial molecular weight of the organic liquid hydrogen storage material plus the molecular weight after n x 2H.
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