Gas analysis device with improved separating arrangement for molecular hydrogen

Abstract

Th invention relates to a gas analysis device (10) for analysing a substance sample (15) which contains molecular hydrogen (16). The device comprises a separating arrangement (20) having at least one separating device (21) which is connected downstream to a measuring device (24). According to the invention, the gas analysis device (10) is provided with a first separating device (21) which comprises a first line (31) which is at least partially permeable for molecular hydrogen (16) and is at least partially impermeable for the remainder (18) of the substance sample (15). The measuring device (24) is designed to detect a mass flow (27) and / or volume flow of the molecular hydrogen (16). The invention also relates to a method (100) for detecting a composition of a substance sample (15) by means of such a gas analysis device (10) and to use according to the invention of non-graphitic carbon. The invention also relates to a method (200) for simulating an operating behaviour of such a gas analysis device (10) and to a simulation program product (60) suitable for this.

Description

[0001] Description

[0002] Gas analysis device with improved separation arrangement for molecular hydrogen

[0003] The invention relates to a gas analysis device for analyzing a substance sample containing molecular hydrogen. The invention also relates to a method for determining the composition of a substance sample containing molecular hydrogen. Furthermore, the invention relates to the use of non-graphitic carbon, a simulation method, and a simulation program product.

[0004] From the article "Green Hydrogen: Transport in the Natural Gas Network," p. 1 | 3, Research Compact, April 1, 2021, by the Fraunhofer Society, a carbon coating is known that allows hydrogen to be separated from a mixture with natural gas. For this purpose, the natural gas-hydrogen mixture is introduced into a number of lines contained within a pipe.

[0005] WO 2012 / 000727 A1 discloses a device for separating gases, comprising membrane separation stages. This includes a feedstream separation stage that separates a feedstream of at least two components into a first permeate stream and a first retentate stream. A plurality of such membrane separation stages are interconnected therein.

[0006] Gas analysis devices are increasingly being used in applications in which substance samples containing molecular hydrogen are to be analyzed. At the same time, there are high demands on the safety of operating gas analysis devices. There is therefore a need for a method suitable for analyzing substance samples containing molecular hydrogen precisely and safely. This object is achieved by a gas analysis device according to the invention which is designed to analyze a substance sample containing molecular hydrogen. The gas analysis device comprises a separation arrangement which includes at least one first separation device. The substance sample can flow through the separation arrangement during operation. The gas analysis device is connected downstream of the separation arrangement to at least one measuring device.According to the invention, the first separation device comprises at least a first line which is at least partially permeable to molecular hydrogen. The first line has a wall through which molecular hydrogen can pass. Likewise, the first line is at least partially impermeable to a residue of the substance sample, i.e. all other components of the substance sample. The first line is thus designed such that molecular hydrogen escapes from the first line when it flows through it. Correspondingly, the first line is designed so that the residue of the substance sample remains in the first line when the substance sample flows through the first line. Furthermore, the measuring device is designed and connected to the separation arrangement to detect a mass flow and / or volume flow of the molecular hydrogen which is separated from the substance sample by the separation arrangement.

[0007] The separation arrangement of the gas analysis device according to the invention is thus suitable for passively separating the molecular hydrogen from the substance sample. This eliminates the need for active components in the separation arrangement, which could, for example, cause electrical discharges. The separation of the molecular hydrogen is essentially driven by a delivery pressure with which the substance sample is fed to the separation arrangement. The separation arrangement, and thus also the first separation device, can therefore be manufactured particularly simply and cost-effectively. Furthermore, a mass flow and / or a volume flow can be measured reliably and precisely in a simple manner. Based on the measured mass flow and / or volume flow of the molecular hydrogen, its proportion in the substance sample can thus be determined in a simple manner.For example, the mass flow and / or volume flow of the hydrogen can be related to a dosing specification by means of which a mass flow and / or volume flow of the substance sample is obtained which is fed to the separation arrangement during operation. For this purpose, the gas analysis device can be provided with an evaluation unit which is connected at least to the measuring device with which the mass flow and / or volume flow of the molecular hydrogen can be detected. A measuring device with which a mass flow is detected can be designed to detect an absolute mass fraction of the molecular hydrogen. For this purpose, the measuring device can be provided with a pressure regulating device. Alternatively or additionally, the measuring device can be designed as a rotameter. The volume flow of the molecular hydrogen can be detected by means of a rotameter.Such a measuring device offers an increased level of explosion protection and allows particularly safe operation of the gas analysis device.

[0008] In one embodiment of the claimed gas analysis device, the first separation device can comprise a second line which is designed to receive the molecular hydrogen passing through the first line. The second line can be designed substantially as a pipeline in which the first line is received and is thus surrounded by the second line. The second line can be connected to the measuring device with which the mass flow and / or volume flow of the molecular hydrogen can be detected. The first and second lines can have inner diameters such that a gap between the first and second lines is minimized. The smaller the gap between the first and second lines, the faster the mass flow or volume flow of the molecular hydrogen follows a change in the proportion of molecular hydrogen in the substance sample.Lines, in particular pipelines, can be easily adapted structurally in order to measure the proportion of molecular hydrogen. Furthermore, by adjusting the diameters, i.e. the inner and outer diameters of the first and second lines, the surface through which the molecular hydrogen escapes from the first line can be adjusted. The claimed gas analysis device can therefore be easily adapted structurally in terms of separation behavior and is therefore suitable for a wide range of applications. Furthermore, pipelines are cost-effectively available in a wide range of dimensions, whereby the separation arrangement of the claimed gas analysis device can be manufactured economically.

[0009] Furthermore, the first line can be coated in its inner wall, at least in sections, with a coating which is at least partially made of non-graphitic carbon, in particular with carbon that forms a turbostratic structure. The coating can also be made entirely of non-graphitic carbon, in particular carbon that forms a turbostratic structure or is designed as a turbostratic structure. Such coatings with or made of non-graphitic carbon are at least partially permeable to molecular hydrogen and essentially impermeable or at least partially impermeable to molecules that are larger than molecular hydrogen. Furthermore, the wall of the first line can be made at least partially from a polymer, a ceramic or a combination thereof.This ensures an overall permanent filter effect, by means of which the molecular hydrogen can be effectively separated from the remaining substance sample. Alternatively or additionally, the first line can be coated on its inner wall, at least in sections, with a coating which is made at least partially from an amorphous or semi-crystalline plastic, for example polyimide, polyamide, polysulfone, cellulose acetate and derivatives thereof, polyphenylene oxides, polysiloxane, polymer with intrinsic microporosity, mixed matrix membranes, facilitated transport membranes, polyethylene oxide, polypropylene oxide or mixtures thereof. In addition, the separation arrangement can comprise a second separation arrangement. The second separation arrangement is arranged in series behind the first separation device or arranged in cascade with the first separation device.In a serial arrangement of the second separation device, the remaining material sample from the first separation device is fed to it. The second separation device can, analogously to the first separation device, comprise a first line which is surrounded by a second line and whose inner wall is coated at least in sections with non-graphitic carbon. Correspondingly, alternatively, the first line of the second separation device can have its inner wall at least in sections coated with a coating which is at least partially made of an amorphous or semi-crystalline plastic, for example polyimide, polyamide, polysulfone, cellulose acetate and derivatives thereof, polyphenylene oxides, polysiloxane, polymer with intrinsic microporosity, mixed matrix membranes, facilitated transport membranes, polyethylene oxide, polypropylene oxide or mixtures thereof.Furthermore, the dimensions of the second separation device can be adapted, for example with regard to the internal diameter of its first line. The remaining substance sample discharged from the first separation device has a reduced proportion of molecular hydrogen, to which the second separation device can be adapted. The molecular hydrogen separated by the second separation device can be combined with the molecular hydrogen separated in the first separation device and the resulting mass flow and / or volume flow can be recorded using the measuring device. The measuring device is arranged accordingly to record the combined mass flow or volume flow of molecular hydrogen. By means of such a serial design of the separation arrangement, an increased separation effect is achieved and the proportion of molecular hydrogen in the remainder of the substance sample that can be discharged from the second separation device is reduced.This further increases the operational reliability of the gas analysis device, particularly during further analysis of the remaining substance sample.

[0010] Alternatively or additionally, the second separation device can be connected in cascade to the first separation device. In the cascading arrangement, the molecular hydrogen separated in the first separation device is fed to the second separation device. The second separation device can, as in the serial arrangement, be designed to correspond to the first separation device. In the cascading arrangement of the second separation device, foreign components are separated from a flow containing predominantly molecular hydrogen. This increases the purity of the molecular hydrogen, for which the mass flow and / or volume flow is to be recorded. In particular, when the mass flow is recorded, this prevents falsification of the measurement result. In particular, it is avoided that an apparently increased mass flow is present.In the cascading arrangement of the first and second separation devices, the foreign components remaining in the second separation device can be combined with the remaining sample which is discharged from the first separation device. The cascading arrangement of the first and second separation devices results in increased measurement accuracy when determining the proportion of molecular hydrogen in the sample. Furthermore, the serial and cascading arrangements can be combined by including at least a third separation device. This allows the separation efficiency of the separation device to be easily scaled and adapted to the respective application.

[0011] In a further embodiment of the claimed gas analysis device, the first line of at least one of the separation devices can be designed as a multiple line. The first line can therefore have a plurality of closed line cross-sections which form a bundle of lines. As a multiple line, the first line can have a plurality of line sections which are arranged essentially parallel to one another. The closed line cross-sections can, for example, be essentially circular. By means of such a multiple line, a line cross-section of the second line surrounding the first line can be filled more fully. Furthermore, a surface area through which molecular hydrogen can pass from the first line into the second line is thus increased. This accelerates the separation of the molecular hydrogen from the substance sample.As a result, an increase in the proportion of molecular hydrogen in the sample can be detected at an accelerated rate. This allows the claimed gas analysis device to be used in safety-critical applications, for example, in monitoring an electrolyzer or a sensitive chemical production process.

[0012] In addition, the first line in the claimed gas analysis device can be provided with, i.e. connected to, a further measuring device which is designed to record a mass flow and / or volume flow of the remainder of the substance sample. The remainder of the substance sample or the remaining substance sample corresponds to the substance sample fed to the separation arrangement, from which the molecular hydrogen contained therein is separated. In conjunction with the measuring device which is connected to the second line, the proportion of molecular hydrogen in the substance sample can thus be determined by comparing the mass flows or volume flows of molecular hydrogen and the remainder of the substance sample. If the composition of the substance sample changes, i.e. if the proportion of molecular hydrogen changes, the mass flows or volume flows quickly follow the change in composition.Accordingly, for example, a rapid increase in the proportion of molecular hydrogen can be detected early on. This makes the claimed gas analysis device also suitable for monitoring safety-critical applications. Alternatively or additionally, a further measuring device can be connected to the separation arrangement on the supply side and designed to measure a total mass flow of the sample. The proportion of molecular hydrogen in the sample can be determined accordingly by reference to the total mass flow.

[0013] Furthermore, the claimed gas analysis device can be provided with a detector which is designed to analyze the remaining substance sample from the separation arrangement. The detector can for this purpose be connected directly or indirectly to at least one of the lines of the first and / or second separation device. The detector can be designed, for example, as a flame ionization detector, as a thermal conductivity detector, as a photoionization detector, as a flame photometric detector, as an electron capture detector, as an atomic emission detector, as a plasma detector, as a mass spectrometer, ion mobility spectrometer and / or mass spectrometer. Furthermore, the gas analysis device can be provided with at least one separation column which can be mounted, for example, downstream of the separation arrangement. The separation column is further preferably positioned upstream of the detector.By separating molecular hydrogen from the sample, the remaining sample can be advantageously used in detectors in which the sample is ignited or exposed to an energy discharge. Consequently, samples containing molecular hydrogen can be safely handled with the claimed gas analysis device. Furthermore, the claimed gas analysis device can be combined with a wide range of analytical concepts, making it versatile.

[0014] The problem described at the outset is also solved by a method according to the invention for determining the composition of a substance sample which contains molecular hydrogen. For this purpose, a gas analysis device is used. The method comprises a first step in which the substance sample is fed into a first line which is part of a separation arrangement of the gas analysis device. The separation arrangement is designed to separate the molecular hydrogen from the substance sample. The method also includes a second step in which the molecular hydrogen which penetrates a wall of the first line is collected and discharged. The first line is at least partially permeable to molecular hydrogen and at least partially impermeable to the rest of the substance sample, i.e. the remaining substance sample. The first line can be accommodated in a second line.This allows the molecular hydrogen passing through the wall of the first line to be collected and removed in the second line. The remaining sample is passed on in the second step of the process and, for example, removed from the separation device.

[0015] The method further comprises a third step in which a mass flow and / or volume flow of the removed molecular hydrogen is measured. For this purpose, the molecular hydrogen is fed to a suitable measuring device. Based on the measured mass flow and / or volume flow, a hydrogen content of the sample added in the first step is determined in the third step.

[0016] According to the invention, the first line is coated at least in sections on its inner wall with non-graphitic carbon, in particular with non-graphitic carbon which forms turbostratic structures or is formed as a turbostratic structure. The coating with non-graphitic carbon ensures that only the molecular hydrogen escapes from the first line and that the molecular hydrogen collected and discharged in the second step has an increased purity. It is also ensured that the remaining material sample, i.e. the remainder of the material sample, is essentially free of molecular hydrogen. This enables simple and at the same time precise detection of the hydrogen content, i.e. the proportion of molecular hydrogen, in the material sample. Furthermore, mass flows orVolume flows can be precisely measured even in molecular hydrogen at relatively low temperatures and without significant energy discharges. This increases the operational reliability of the process according to the invention. In the process according to the invention, the material sample can essentially be guided through the separation arrangement by a conveying pressure, which can accordingly be made from passive components. A passive component is understood here to be any component that can be operated without a power supply. By separating the molecular hydrogen from the rest of the material sample, its handling is also further simplified.

[0017] In one embodiment of the claimed method, the gas analysis device on which the method is carried out can be designed according to one of the embodiments outlined above. The features of the gas analysis device also apply analogously to the claimed method. In particular, the remainder of the sample, i.e. the remaining sample, can be fed to a separation column, behind which a detector is arranged. In a fourth method step, the remainder of the sample can thus be analyzed for its composition. The technical advantages of the claimed gas analysis device also apply overall to the claimed method.

[0018] The object outlined above is also achieved by the inventive use of non-graphitic carbon, in particular turbostratic carbon. The non-graphitic carbon is used to separate molecular hydrogen from a substance sample flowing through a first line. The first line can be accommodated in a second line. The non-graphitic carbon is applied as a coating to an inner wall of the first line. According to the invention, the first line belongs to a separation arrangement of a gas analysis device. The gas analysis device is designed to determine a composition of the substance sample.The invention is based, among other things, on the surprising discovery that a coating with non-graphitic carbon allows such a pure separation of the molecular hydrogen in the sample that its content can be measured with a precision sufficient not only for industrial purposes but also for analytical purposes. The inventive use of non-graphitic carbon thus makes it possible to improve the safety and simplify the design of gas analysis devices that analyze hydrogen-containing samples.

[0019] In one embodiment of the claimed use, the gas analysis device, which includes the first conduit coated with the non-graphitic carbon, is designed as a gas analysis device according to one of the embodiments outlined above. The features of the gas analysis device are thus transferable to the claimed use and achieve the same technical advantages.

[0020] Furthermore, the object described at the outset is achieved by a method according to the invention for simulating the operating behavior of a gas analysis device. The method comprises a first step in which a data set is provided by which at least the first line is simulated at least in section. The data set can include a structure of the first line, i.e. its geometry and / or material properties. Overall, the data set represents a virtual representation of at least the first line. Furthermore, the method according to the invention comprises a second step in which at least one operating parameter is specified by which the operating behavior to be simulated is defined. The operating parameter can be specified by a user of the method, an algorithm, and / or another simulation-oriented computer program.The operating parameter can, for example, specify the composition of a substance sample to be analyzed by the gas analysis device, its dosage, i.e., its quantity, its temperature, pressure, and / or flow rate. Likewise, the at least one operating parameter can include information about ambient conditions, for example, an ambient temperature and / or an ambient pressure.

[0021] The method also includes a third step in which a simulation program product is executed which is designed to determine a performance parameter of the simulated gas analysis device based on the data set from the first step and the at least one operating parameter from the second step. The performance parameter can be any variable that results from the substance sample flowing through the first line. The performance parameter can, for example, be an amount of molecular hydrogen that penetrates the wall of the first line and / or a time until a predeterminable degree of separation occurs between the molecular hydrogen and the remaining substance sample. When the simulation program product is executed, a virtual representation of the substance sample with the molecular hydrogen is provided which flows through at least the first line, i.e. its virtual representation.In the third step of the method, the at least one performance parameter is further determined by the simulation program product. Furthermore, the method includes a fourth step in which the performance parameter determined in the third step is output to a user and / or a data interface. The data interface can be configured to forward the data set, the at least one operating parameter, and / or the at least one performance parameter to another simulation-oriented computer program.

[0022] According to the invention, the gas analysis device whose operating behavior is simulated is designed according to one of the embodiments described above. The invention is based, inter alia, on the surprising discovery that the permeation behavior of molecular hydrogen through the wall of the first line can be simulated quickly and precisely in a simple manner. Permeation of other components of the substance sample is negligible, thereby reducing the simulation effort. Furthermore, the distribution of the molecular hydrogen in a line cross-section in the substance sample can be represented as a uniform distribution. This makes it possible, for example, to utilize a rotational symmetry of the first line. The permeation behavior in a line cross-section can essentially be modeled as one-dimensional behavior.By stringing together a number of line cross-sections along a line axis which runs through the centre points of the line cross-sections, the permeation behaviour of the molecular hydrogen can be simulated in a simplified manner. The permeation behaviour of the hydrogen through the wall of the first line can be reproduced using a predeterminable number of line cross-sections along the first line. The number of line cross-sections taken into account can be reduced because the permeation behaviour between two line cross-sections can be interpolated with increased accuracy. Accordingly, the operating behaviour of the first line, and thus of the gas analysis device, can be simulated precisely and quickly. In particular, real-time capability can be achieved for the method according to the invention. Consequently, the method according to the invention is suitable for monitoring the operation of the gas analysis device during operation.This allows damage to components of the gas analysis device, for example the first line, to be detected at an early stage, which enables safe operation of the gas analysis device.

[0023] The object set out above is achieved by a simulation program product according to the invention. The simulation program product is designed to simulate the operating behavior of a gas analysis device. According to the invention, the simulation program product is designed to implement a method, i.e. a simulation method, according to one of the embodiments outlined above. For this purpose, the simulation program product can be designed as a digital twin of the gas analysis device, as described in more detail, for example, in the document US 2017 / 286572 A1. The disclosure content of US 2017 / 286572 A1 is incorporated by reference into the present application. The simulation program product can comprise a physics module which is designed to simulate the permeation behavior of a gas through a solid body, for example a wall.Alternatively or additionally, the physics module can be designed to simulate the flow behavior of a gas in a line. The simulation program product can be monolithic, i.e., executable entirely on a single hardware platform. Alternatively, the simulation program product can be modular, i.e., comprise a plurality of subprograms that can be executed on separate hardware platforms and interact via a communicative data connection. Such a communicative data connection can be a network connection, an internet connection, and / or a mobile radio connection.

[0024] The invention is explained in more detail below with reference to individual embodiments in the figures. The figures are to be read as complementary to one another in that identical reference numerals in different figures have the same technical meaning. Furthermore, the individual features of the embodiments shown in the figures can also be combined with one another and with the features outlined above. They show in detail:

[0025] FIG 1 shows a schematic structure of an embodiment of the claimed gas analysis device;

[0026] FIG 2 shows a schematic section of a structure of a first embodiment of the first separating device;

[0027] FIG 3 is a schematic representation of the first embodiment of the first separating device in longitudinal section;

[0028] FIG 4 is a schematic representation of a second embodiment of the first separation device in an oblique view. FIG 1 schematically shows the structure of an embodiment of the claimed gas analysis device 10. Likewise schematically shows the sequence of a method 100 for determining the composition of a substance sample 15, which is carried out on the gas analysis device. The gas analysis device 10 has a gas inlet 11, via which the substance sample 15 can be supplied. The gas inlet 11 is connected to a separation arrangement 20, which is designed to separate molecular hydrogen 16 from the substance sample 15. The separation arrangement 20 comprises a first separation device 21 and a second separation device 22, which are connected to one another in a cascade. The first and second separation devices 21, 22 are essentially structurally identical. The first separating device 21 is designed to separate the material sample

[0029] 15 molecular hydrogen 16 to separate. The molecular hydrogen 16 separated by the first separation device 21 is mixed with the residue 18 of the sample 15 and forms an intermediate filtrate 17. This is fed to the second separation device 22. Correspondingly, the second separation device 22 is designed to separate essentially pure molecular hydrogen 16. Residues 18 of the sample 15 from the first and second separation devices 21, 22 are combined. Accordingly, the molecular hydrogen

[0030] 16 and the remainder 18 of the material sample 15 can be discharged separately from the separation arrangement 20.

[0031] The separation arrangement 20 is connected to a measuring device 24 such that the molecular hydrogen 16 from the separation arrangement 20 can be detected in terms of mass flow and / or volume flow. Correspondingly, the separation arrangement 20 is connected to a further measuring device 26 such that the mass flow and / or volume flow of the residue 18 of the substance sample 15 can be detected. The measuring devices 24, 26 are further connected to an evaluation unit 40 which evaluates the detected mass flows 25, 27 of molecular hydrogen 16 and the residue 18 of the substance sample 15. For this purpose, suitable measurement signals 29 are sent to the evaluation unit 40. By comparing the mass flow 25 of molecular hydrogen 16 with the mass flow 27 of the residue 18 of the sample 15, the proportion of molecular hydrogen 16 in the sample 15 can be determined. The evaluation unit 40 is equipped with a suitable computer program 45 for this purpose.

[0032] The gas analysis device 10 also has a separation column 12, which is connected downstream of the separation arrangement 20 and the further measuring device 26, i.e. is located downstream of them. The residue 18 of the substance sample 15 can be fed to the separation column 12 and separated into its components by retention. The separation of the residue 18 of the substance sample 15 is symbolized by a chromatogram 19. Furthermore, a detector 30 is connected to the separation column 12, which is designed to detect and / or quantify the components of the residue 18 of the substance sample 15. In order to evaluate the measurements of the detector 30, the latter is connected to the evaluation unit 40 via a communicative data connection, via which corresponding measurement signals 2 can be transmitted. Downstream of the detector 30, the remainder 18 of the substance sample 15 can be removed from the gas analysis device 10 via a gas outlet 13.Analogously, the molecular hydrogen 16 can be discharged from the gas analysis device 10 via a gas outlet 13 downstream of the measuring device 24.

[0033] The evaluation unit 40 is further connected to a display unit 46 and a data interface 48. Via this display unit 46, results of the recording of the composition of the substance sample 15 can be transmitted to a user or to another computer program product. Furthermore, a simulation program product 60 is stored in an executable manner from the evaluation unit 20, which is designed as a digital twin of at least the separation arrangement 20 and with which the operation of the gas analysis device 10 can be monitored. The simulation program product 60 is designed for this purpose to carry out a simulation method 200 (not shown in detail). With the gas analysis device 10 shown, a method 100 for determining a composition of the substance sample

[0034] 15 can be carried out. In a first step 110 of the method 100, the substance sample 15 is fed via the gas inlet 11 and guided to the separation arrangement 20. In the separation arrangement 20, the substance sample 15 is separated in a second step 120 essentially into molecular hydrogen 16 and the remainder 18 of the substance sample 15. This is followed by a third step 130, in which the mass flow 25 of the molecular hydrogen 16 is recorded by means of a measuring device 24. Likewise, in the third step 130, a mass flow 27 of the remainder 18 of the substance sample 15 is recorded with a further measuring device 26. Likewise, in the third step 130, based on the mass flows 25, 27, the proportion 35 of molecular hydrogen

[0035] 16 in the material sample 15 is determined. For this purpose, the computer program product 45, which is executably stored on the evaluation unit 40, is used. The determined proportion 35 of molecular hydrogen 16 in the material sample 15 is output via the display unit 46 and / or the data interface 48.

[0036] The structure of the separation device 20 , which enables the underlying separation of the molecular hydrogen 16 from the material sample 15 , is shown and described in more detail below.

[0037] FIG. 2 schematically shows a section of the structure of a first embodiment of the first separation device 21, which can be used in a gas analysis device 10, as shown in FIG. 1. The second separation device 22 can also be designed to correspond to the first separation device 21, or any further separation device in a separation arrangement 20 in a gas analysis device 10, as in FIG. 1. A method 100, as shown in FIG. 1, can also be implemented using the first separation device 21 shown.

[0038] The first separation arrangement 21 comprises at least a first line 31, which is surrounded by a second line 32. The first and second lines 31, 32 each have a wall 33 and are essentially tubular. Likewise, the first and second lines 31, 32 have a essentially circular line cross-section 44. The inner diameter 37 of the first line 31 is smaller than the inner diameter 39 of the second line 39. The first line 31 is thus surrounded by the second line 32 and a gap 38 is formed between them. During operation of the first separation device 21, a substance sample 15 is fed to the first line 31, which substance sample comprises molecular hydrogen 16 and a residue 18 of the substance sample 15. The residue 18 of the substance sample 15 can comprise a plurality of components. The material sample 15 is fed to the first line 31 in the first step 110 of the method 100, as shown in FIG 1.The first line 31 is at least partially provided on its inner wall 34 with a coating 42, which is at least partially made of non-graphitic carbon, in particular of carbon that forms a turbostratic structure or is formed as a turbostratic structure. The coating 42 is essentially permeable to the molecular hydrogen 16, so that the molecular hydrogen 16 penetrates the wall 33 of the first line 31, i.e., passes through the wall 33 into the intermediate space 38. The coating 42 is essentially impermeable to the remainder 18 of the sample 15. Along a flow direction 28, the amount of molecular hydrogen 16 in the sample 15 in the first line 31 thus decreases. Correspondingly, the amount of molecular hydrogen 16 in the second line 32 increases.The flow of the substance sample 15, i.e. the molecular hydrogen 16 and the residue 18, is driven by a delivery pressure 23, with which the substance sample 15 is fed to the corresponding separation arrangement 20. The molecular hydrogen 16 in the second line 32 can be discharged separately from the intermediate space 38, i.e. the second line 32. Likewise, the remaining residue 18 of the substance sample 15 can be discharged separately from the first line 31. The respective mass flow and / or volume flow of the molecular hydrogen 16 and the residue 18 of the substance sample 15 can thus be recorded by separate measuring devices 24, 26, as shown by way of example in FIG. 1.

[0039] For a better overview, FIG. 2 shows an idealized separation process. In an embodiment such as that shown in FIG. 1, an ideal separation is not achieved, at least in the first separation device 21. Rather, admixtures of the residue 18 of the sample 15 in the molecular hydrogen 16 are to be expected.

[0040] At least the first line 31 is stored as a virtual representation in a simulation program product 60 as a data set. The simulation program product 60 is designed as a digital twin of at least the first line 31 and is configured to simulate its operating behavior in the course of a simulation method 200 (not shown in detail).

[0041] The first embodiment of the first separation device 21 according to FIG. 2 is shown schematically in FIG. 3 in a longitudinal section. The first separation device 21 belongs to the separation arrangement 20 of a gas analysis device 10. A second separation device 22 of the separation arrangement 20 can be designed to correspond to the first separation device 21 shown. The features shown in FIG. 3 thus also apply analogously to a second separation device 22.

[0042] The first separation device 21 comprises the first line 31, which is surrounded by the second line 32. The material sample 15, which has molecular hydrogen 16 and a residue 18, is fed to the first line 31 by a feed pressure 23 along a line axis 45, wherein the residue 18 can comprise several components, i.e. different substances. The inside of the wall 33 of the first line 31, i.e. its inner wall 34, is at least partially provided in sections with the coating 42, which is at least partially made of non-graphitic carbon. The coating 42 is at least partially permeable to the molecular hydrogen 16 and essentially impermeable to the residue 18 of the material sample 15.When flowing through the first line 31, the molecular hydrogen 16 passes through the coating 42 and the wall 33 of the first line and enters an intermediate space 38 which is defined by the walls 33 of the first and second lines 31, 32. Along the line axis 45, the amount of molecular hydrogen 16 decreases in the first line 31 and increases correspondingly in the second line 32, i.e. in the intermediate space 38. The inner diameter 37 of the first line 31 and the inner diameter 39 of the second line 32 are dimensioned, taking into account the wall thickness of the wall 33 of the first line 31, in such a way that effective removal of the molecular hydrogen 16 which has entered therein is ensured. The first line 31 is dimensioned such that the inner wall 34 with the coating 42 has a maximized surface, thereby assisting the separation of the molecular hydrogen 16 from the rest 18 of the substance sample 15.The discharge pressure 23 ensures the removal of the residue 18 of the sample 15 and the molecular hydrogen 16 along the flow direction 28.

[0043] For a better overview, FIG. 3 shows an idealized separation process, corresponding to FIG. 2. In an embodiment such as that shown in FIG. 1, an ideal separation is not achieved, at least in the first separation device 21. Rather, admixtures of the residue 18 of the sample 15 in the molecular hydrogen 16 are to be expected.

[0044] The separation behavior of the molecular hydrogen 16 from the residue 18 of the substance sample 15 is simulated in a simulation process 200 which is carried out using the simulation program product 60. The simulation program product 60 comprises a data set in which the structure of at least the first line 31 is mapped. The delivery pressure 23, the amount of substance sample 15 supplied and its composition can be specified as operating parameters. As performance parameters, the simulation program product 60 can be used to determine a quantity and / or a purity of the molecular hydrogen 16 which is discharged from the intermediate space 38, i.e. the second line 32. Alternatively or additionally, the quantity and / or a purity of the residue 18 of the substance sample 15 which is discharged from the first line 31 can be determined using the simulation program product 60.For this purpose, the permeation behavior 41 of the molecular hydrogen 16 through the wall 33 of the first line 31 is simulated with the coating 42 at a plurality of line cross-sections 44. The permeation behavior 41 is simulated as a one-dimensional permeation behavior 41 for each line cross-section 44. Since the remainder 18 of the substance sample 15 consists of larger molecules than hydrogen molecules, the coating 42 is essentially impermeable to the remainder 18, so that a simulation of the permeation behavior of the remainder 18 is unnecessary. Because the first line 31 is essentially rotationally symmetrical, the one-dimensionally simulated permeation behavior 41 can be easily transferred to the entire line cross-section 44. In order to simulate the permeation behavior 41 along the first line 31 in the flow direction 28, this is determined for a plurality of spaced line cross sections 44 which serve as support points.An interpolation 43 is performed between the corresponding line cross-sections 44, by which the permeation behavior 41 can be reproduced with sufficient precision in the sections between the line cross-sections 44. The simulation program product 60 is therefore suitable for quickly reproducing the operating behavior of the first separation device 21 with reduced computational effort, thereby resulting in real-time capability for the corresponding simulation method 200 for a wide range of applications.

[0045] A first separation device 21 according to a second embodiment of the claimed gas analysis device 10 is shown schematically in an oblique view in FIG 4. The first separation device 21 belongs to a separation arrangement 20. A second separation device 22 of the separation arrangement 20 can be designed to correspond to the first separation device 21. The first separation device 21 comprises a plurality of first lines 31, which are designed as multiple lines. The first line 31 comprises a plurality of essentially circular line cross-sections 44, which are each delimited by a wall 33. The multiple line is designed essentially in the shape of a bundle, so that a surface of inner walls 34 with a coating 42 is maximized. The individual lines of the multiple line can be of identical construction or of different types.As a result, the multiple line can be adapted to a wide range of applications, for example by adjusting the diameters of the individual lines. The coating 42 is made at least partially from a non-graphitic carbon, in particular one that forms turbostratic structures or is designed as a turbostratic structure. The structure of the individual line cross sections 44 can each correspond to a structure as in FIG 3. The first line 31 designed as a multiple line is surrounded by a second line 32. Between the line cross sections 44 of the first line 31 and the second line 32 there is formed an intermediate space 38 through which separated molecular hydrogen 16 can be discharged.The first line 31 according to FIG 4 is depicted in a simulation program product 60 which is designed as a digital twin and with which a simulation method 200 can be carried out with which the operating behavior of the associated gas analysis device 10 can be reproduced.

Claims

Patent claims 1. A gas analysis device (10) for analyzing a substance sample (15) containing molecular hydrogen (16), comprising a separation arrangement (20) with at least one first separation device (21) connected downstream to a measuring device (24), wherein the first separation device (21) comprises a first line (31) that is at least partially permeable to molecular hydrogen (16) and at least partially impermeable to a residue (18) of the substance sample (15), wherein the measuring device (24) is designed to detect a mass flow (27) and / or volume flow of the molecular hydrogen (16); characterized in that the first separation device (21) comprises a second line (32) that is designed to receive the molecular hydrogen (16) passing through the first line (31), and in which the first line (31) is received.

2. Gas analysis device (10) according to claim 1, characterized in that the first line (31) is coated on its inner wall (34) at least in sections with a coating (42) which is made at least partially of non-graphitic carbon.

3. Gas analysis device (10) according to claim 1 or 2, characterized in that the non-graphitic carbon forms a turbostratic structure.

4. Gas analysis device (10) according to one of claims 1 to 3, characterized in that the separating arrangement (20) comprises a second separating device (22) which is connected in series or in cascade to the first separating device (21).

5. Gas analysis device (10) according to one of claims 1 to 4, characterized in that the first line (31) is designed as a multiple line.

6. Gas analysis device (10) according to one of claims 1 to 5, characterized in that the first line (31) is provided with a further measuring device (26) which is designed to detect a mass flow (27) and / or volume flow of a residue (18) of the material sample (15).

7. Gas analysis device (10) according to one of claims 1 to 6, characterized in that the gas analysis device (10) is provided with a detector (30).

8. A method (100) for determining a composition of a substance sample (15) containing molecular hydrogen (16) by means of a gas analysis device (10), comprising the steps of: a) feeding the substance sample (15) into a first line (31) of a separation arrangement (20) of the gas analysis device (10); b) collecting and removing the molecular hydrogen (16) which penetrates a wall (33) of the first line (31) in a second line (32) in which the first line (31) is accommodated, and passing on the remaining substance sample (15); c) detecting a mass flow (27) and / or volume flow of the removed molecular hydrogen (16) and, based thereon, determining a hydrogen content (35) in the supplied substance sample (15); wherein the first line (31) is coated at least in sections on its inner wall (34) with non-graphitic carbon.

9. Method (100) according to claim 8, characterized in that the gas analysis device (10) is designed according to one of claims 1 to 7.

10. Use of non-graphitic carbon, in particular carbon which forms a turbostratic structure, for separating molecular hydrogen (16) from a material sample (15), as a coating (42) of a first line (31), characterized in that the first line (31) to a separating arrangement (20) of a gas analysis device (10), wherein the first line (31) is accommodated in a second line (32).

11. Use of non-graphitic carbon according to claim 10, characterized in that the gas analysis device (10) is designed according to one of claims 1 to 7.

12. A method (200) for simulating an operating behavior of a gas analysis device (10), comprising the steps of: a) providing a data set by which at least the first line (31) is adjusted at least in sections; b) specifying at least one operating parameter by which the operating behavior to be simulated is defined; c) executing a simulation program product (60) which is designed to determine a performance parameter of the simulated gas analysis device (10) based on the data set and the at least one operating parameter, and determining the performance parameter; d) outputting the determined performance parameter to a user and / or a data interface; characterized in that the gas analysis device (10) is designed according to one of claims 1 to 7.

13. Simulation program product (60) for simulating an operating behavior of a gas analysis device (10), characterized in that the simulation program product (60) is designed to carry out a method (200) according to claim 12.

Images