DEVICE AND METHOD FOR PARTIALLY TRANSFERRING A MULTI-COMPONENT LIQUID SAMPLE INTO THE GAS PHASE, AND USE OF THE DEVICE IN THE METHOD

Description

[0001] The invention relates to a device and method for the partial conversion of a liquid sample comprising several components into the gas phase. The invention further relates to the use of the device as a sample preparation device.

[0002] Technical process plants in the chemical and pharmaceutical industries, used for the production of a wide variety of products and medications, as well as water and solvent purification systems, are currently monitored online using simple, integrated process parameters such as pressure, temperature, and light absorption via specific sensors. However, differential reactions in these systems, such as the formation of byproducts, are only detected through offline product control, which is carried out in a laboratory setting. Examples include the formation of byproducts such as diacetyl in beer fermentation or azotoluidine in protein separation columns, as well as the formation of toxins in other processes.

[0003] Another example of undesirable processes is engine oil dilution in internal combustion engines, particularly those in motor vehicles. The engine oil in an internal combustion engine can be diluted by ethanol-containing fuel, such as Super E10, or diesel fuel containing biodiesel, which can significantly alter its lubricating properties. These changes in the engine oil's properties can negatively affect the internal combustion engine and cause damage.

[0004] Increasing pressure to optimize processes and higher quality demands on process plants necessitate stricter monitoring of the aforementioned undesirable side reactions and the potential formation of unwanted impurities in the products. The products or impurities formed from these side reactions can be liquid or gaseous.

[0005] In the detection of gaseous compounds, gas phase measuring devices, such as flame ionization detectors, fluorescence measuring devices and mass spectrometers, have established themselves as the most sensitive and fastest detection systems.

[0006] The problem remains, however, that undesirable and / or toxic byproducts can form undetected in processes and cannot be detected immediately or within a short time. The same applies to undesirable side processes, such as the aforementioned engine oil dilution. In current technology, samples are often taken at regular intervals or randomly, which are then usually sealed or otherwise treated before being analyzed in a laboratory. This process, however, sometimes results in significant time losses between sampling and receiving the analysis results from the laboratory. Consequently, it is not possible to react immediately to the formation of undesirable and / or toxic byproducts in the process. Such processes, where the sample is taken and subsequently analyzed in a laboratory, can therefore also be described as "offline processes."

[0007] Analyzing liquid samples can be time-consuming if unwanted byproducts or impurities are also present in the liquid state. Therefore, there is a need for suitable and improved devices for the online preparation and analysis of such samples. US 2014 / 084154 A1 describes a device for supplying gaseous sample ions / molecules from liquid droplets containing sample ions / molecules. DE 10 2011 081 287 A1 describes a micro-sampling system for small quantities of fluid samples for vapor-phase analysis, which has several integrated functional units and is suitable for small sample volumes with fast response times.

[0008] It is therefore an object of the present invention to provide a device for the partial conversion of a liquid sample comprising several components into the gas phase according to claim 1, which avoids the disadvantages of known devices of the prior art.

[0009] Furthermore, the object of the present invention is to provide a method for the partial conversion of a liquid sample comprising several components into the gas phase according to claim 6, which avoids the disadvantages of known prior art devices.

[0010] The invention is based on the finding that the above-mentioned problems can be solved with the help of a chamber in which, at a given temperature, an equilibrium is quickly established between the gas and liquid phases of a liquid sample introduced into the chamber, i.e. within 30 seconds, or within 20 seconds, or within 10 seconds.

[0011] The invention therefore provides a device for the partial conversion of a liquid sample comprising several components into the gas phase, which (a) a heatable chamber in which a gas / liquid two-phase or multi-phase system is generated, comprising (a1) a liquid inlet opening for the inlet of the liquid sample, (a2) a liquid outlet opening for the outlet of liquid components not converted into the gas phase, and (a3) ​​a gas phase outlet opening for the outlet of the generated gas phase from the chamber, and (b) a device for controlling the flow rate of the liquid sample into the liquid inlet opening from 1 µl / min to 3000 µl / min, wherein the chamber has an upper region and a lower region, wherein the gas phase outlet opening is located in the upper region of the chamber, the lower region is connected to the upper region, and wherein the upper region has the shape of a body of revolution with a constant diameter and the lower region has the shape of a body of revolution with a decreasing diameter.

[0012] The device according to the invention has the advantage that it can be directly connected to a process to be monitored, for example, a work or production process. This offers the advantage that the device according to the invention can be used "on-site," particularly for the preparation and processing of samples taken from the process being monitored. Therefore, the liquid sample to be examined and analyzed can be taken directly from such a process, for example, from a reactor, a pipeline, or a container of this process, introduced into the device according to the invention, and prepared or processed there.

[0013] The device according to the invention therefore advantageously enables online sample preparation and online sample processing of liquid samples taken directly from a process, in particular for a downstream analytical device, such as a mass spectrometer.

[0014] In the context of this application, "online" means that the total time from taking the liquid sample from a process to receiving the analysis result from an analytical device is less than 5 minutes, preferably less than 3 minutes, and more preferably less than 1 minute. This means that the liquid sample taken directly from a process can be analyzed practically in "real time".

[0015] However, "online" also means that both the extraction of the liquid sample from the process being monitored and the analysis of the liquid sample take place "on-site". In other words, the liquid sample is extracted directly from the process, i.e., via a fluid connection, introduced into the device according to the invention and pre-treated or processed there, and then optionally analyzed in a downstream analytical device, such as a mass spectrometer.

[0016] A further advantage of the device according to the invention is that the device only extracts small volumes of the liquid sample from the process being monitored, with the volumes being in the range of 10 µl to 400 µl. Extracting such small volumes does not affect the process being monitored.

[0017] Without being bound to theory, the device according to the invention achieves an equilibrium in accordance with the laws of thermodynamics, such that liquid components in a solution at a defined temperature and pressure develop corresponding partial pressures above the liquid solution, which are proportional to the concentrations of the components in the liquid phases. Thus, a gas / liquid two-phase or multi-phase system is established, which is in equilibrium. In other words, the various components of the liquid sample are partially converted into the gas phase, corresponding to their concentrations in the liquid phase of the sample.

[0018] A further advantage of the device according to the invention is that the components of the liquid sample transferred into the gas phase are present in the gas phase only in low concentrations, and therefore no further reactions between the components can occur in the gas phase. Therefore, the gaseous components can, if necessary, be transported over long distances to the downstream analytical device, such as a mass spectrometer, without any change in the concentrations of the components in the extracted gas phase.

[0019] The device according to the invention, as described herein in all embodiments, can therefore also be referred to as a partial pressure generator.

[0020] The gas / liquid two- or multi-phase system, as described above, establishes itself in the chamber. The liquid phase of this two- or multi-phase system can be single-phase, two-phase, or multi-phase.

[0021] The chamber in which the gas / liquid two- or multiphase system is established is located inside the device and can take on various shapes. The chamber has an upper and a lower section, with the lower section being connected to the upper section or the upper and lower sections merging into one another. The upper section of the chamber has the shape of a solid of revolution with a constant diameter, and the lower section of the chamber has the shape of a solid of revolution with a decreasing diameter.

[0022] Preferably, the body of revolution with a constant diameter has the shape of a cylinder, and the body of revolution with a decreasing diameter has the shape of a cone or a frustum of a cone. Preferably, the diameter of the cylinder corresponds to the diameter of the base of the cone or frustum; that is, the base of the cylinder is simultaneously the base of the cone or frustum.

[0023] In a preferred embodiment of the chamber, the upper region has the shape of a cylinder and the lower region the shape of a cone, wherein the diameter of the cylinder corresponds to the diameter of the base of the cone and wherein the liquid drain opening is located at the apex of the cone. This ensures that the liquid phase of the gas / liquid two- or multi-phase system can quickly and efficiently pass through the liquid drain opening and be removed from the chamber or device.

[0024] If the upper part of the chamber is a body of revolution with a constant diameter or if the upper part of the chamber has the shape of a cylinder, then the diameter of the body of revolution or of the cylinder is preferably between 6 mm and 24 mm, more preferably between 8 mm and 22 mm, more preferably between 10 and 20 mm, and most preferably between 12 and 18 mm.

[0025] If the lower part of the chamber is a body of revolution with a decreasing diameter, or if the lower part of the chamber has the shape of a cone or truncated cone, then the diameter of the base of the body of revolution or of the cone or truncated cone is preferably between 6 mm and 24 mm, more preferably between 8 mm and 22 mm, more preferably between 10 and 20 mm, and most preferably between 12 and 18 mm.

[0026] In this case, the diameter of the body of revolution with constant diameter or of the cylinder preferably corresponds to the diameter of the base of the body of revolution with decreasing diameter or of the cone or truncated cone.

[0027] The height of the chamber refers to the longest distance between the upper end of the upper section and the lower end of the lower section. If the upper section of the chamber is cylindrical and the lower section is conical, then the height of the chamber is the distance between the top surface of the cylinder and the apex of the cone, measured perpendicular to the top surface of the cylinder.

[0028] The chamber preferably has a height between 4 mm and 30 mm, more preferably between 6 mm and 28 mm, more preferably between 9 mm and 26 mm, further more preferably between 12 mm and 24 mm, and most preferably between 18 mm and 22 mm.

[0029] Preferably the chamber has a volume of 0.1 to 25 cm³, more preferably 0.5 to 20 cm³, more preferably 0.75 to 15 cm³, more preferably 1 to 10 cm³ and most preferably 2 to 8 cm³.

[0030] The liquid sample is introduced into the chamber through the liquid inlet opening. This opening is preferably located in the lower part of the chamber, more preferably at or near the transition between the upper and lower parts of the chamber.

[0031] The device for regulating the flow rate of the liquid sample into the liquid inlet opening preferably comprises a metering valve, more preferably a spindle valve. More preferably, this device comprises a valve, more preferably a spindle valve. This device regulates the flow rate of the liquid sample into the liquid inlet opening of the chamber. The flow rate is preferably 2 to 2000 µl / min, more preferably 5 to 1750 µl / min, more preferably 10 to 1500 µl / min, more preferably 20 to 1000 µl / min, and most preferably 50 to 500 µl / min.

[0032] Liquid components of the sample that have not transitioned into the gas phase are drained from the chamber via the drain. Preferably, the drain opening for these components is located in the lower part of the chamber, more preferably at the very bottom of the lower chamber. The drain opening is therefore preferably located at the apex of the cone or in the top surface of the truncated cone. To remove the liquid from the chamber more quickly and completely through the drain opening, a pump, such as a peristaltic pump, can be used.

[0033] The components that have transitioned into the gas phase are discharged from the chamber through the gas phase outlet. The gas phase outlet is located in the upper region of the chamber, preferably in the upper half of the upper region.

[0034] The gas phase outlet is preferably connected to an analytical device. The analytical device is preferably a mass spectrometer, in particular a mass spectrometer suitable for the analysis of gaseous components. For the present invention, commercially available or prior art mass spectrometers, for example from EP 0 290 711, EP 0 290 712, DE 196 28 093 and WO 02 / 058106, can be used.

[0035] The connection between the gas phase outlet and the analysis device is preferably a fluid connection. The fluid connection is preferably a capillary, a tube, a hose, or a combination thereof.

[0036] Preferably, the device further comprises a device for regulating the gas phase flow from the gas phase outlet opening from 10 ml / min to 500 ml / min, more preferably 30 ml / min to 400 ml / min, more preferably 50 ml / min to 300 ml / min, more preferably 70 ml / min to 250 ml / min, and most preferably 100 ml / min to 200 ml / min. The device for regulating the gas phase flow from the gas phase outlet opening preferably comprises or consists of a valve.

[0037] The chamber within the device is heatable to achieve an adjustable temperature inside the chamber. Preferably, the device has at least one heating element, more preferably at least two heating elements, and the chamber is heated via its walls. Preferably, the heating element is a heating cartridge. The heating element heats the walls of the chamber from the outside.

[0038] Preferably, the temperature at the warmest position of the walls bounding the chamber is a maximum of 300°C, more preferably a maximum of 275°C, more preferably a maximum of 250°C, more preferably a maximum of 225°C, further more preferably a maximum of 200°C, further more preferably a maximum of 175°C, and most preferably a maximum of 150°C.

[0039] Preferably, the temperature at the warmest position of the walls bounding the chamber is at least 20°C, more preferably at least 25°C, more preferably at least 30°C, further more preferably at least 35°C, further more preferably at least 40°C, and most preferably at least 45°C.

[0040] Preferably, the chamber is heated such that a temperature gradient is established from the upper to the lower region of the chamber. This can be achieved, for example, by positioning the heating element at or near the upper region of the chamber. This creates a temperature gradient within the chamber, with the temperature in the upper region being higher than that in the lower region. The temperature difference between the warmest point in the upper region and the coolest point in the lower region of the chamber is preferably a maximum of 50°C, more preferably a maximum of 40°C, further preferably a maximum of 30°C, further preferably a maximum of 20°C, and most preferably a maximum of 10°C.

[0041] If two, three or more heating elements are used, one heating element is positioned at or near the top of the chamber, as described above, and the other heating elements are positioned around the walls enclosing the chamber.

[0042] Preferably, the walls bounding the chamber comprise a metallic material. Metallic materials are preferred because they possess good thermal conductivity, which ensures rapid heat conduction not only from the heating element to the chamber walls, but also from the walls to the liquid sample inside the chamber. The establishment of gas-liquid equilibrium in the chamber can be influenced over time by appropriate selection of the metallic material. The higher the thermal conductivity of the metallic material, the faster gas-liquid equilibrium can be established in the chamber. Therefore, the metallic materials preferably include iron, steel, stainless steel, aluminum, copper, silver, and their alloys, with stainless steel being even more preferred.In a preferred embodiment, the metallic materials consist of iron, steel, stainless steel, aluminum, copper, silver and their alloys; more preferably, the metallic material consists of stainless steel.

[0043] Preferably, the chamber includes a further liquid inlet opening for introducing a diluting liquid. This liquid inlet opening is preferably located in the lower region of the chamber, more preferably at or near the transition between the upper and lower regions of the chamber. Preferably, the liquid inlet opening for introducing a diluting liquid is located in the same plane, i.e., at the same height or level, of the chamber as the liquid inlet opening for introducing the liquid sample.

[0044] The diluting liquid is used to dilute the liquid sample in the chamber. Preferably, the diluting liquid is the "base substance," i.e., the main component of the liquid sample, as described herein. This additional introduction of the main component into the chamber increases its concentration in the liquid sample, while simultaneously reducing the concentration of one or more minor components. This proves particularly advantageous when the initial concentration of one or more minor components in the liquid sample is too high, which could lead to errors in the analysis and quantitative determination of these components.For the purposes of this application, "original concentration" refers to the concentration of the main and minor components in the liquid sample before any dilution, for example, by diluting liquids and / or (carrier) gases. In other words, the original concentration corresponds exactly to the concentration of the liquid sample as it was taken, for example, from another process or container.

[0045] The device preferably further comprises a device for regulating the flow rate of the diluting liquid into the liquid inlet opening for introducing the diluting liquid. This device preferably comprises a metering valve, for example a spindle valve; more preferably, this device consists of a spindle valve. The flow rate is preferably 1 to 3000 µl / min, more preferably 2 to 2000 µl / min, more preferably 5 to 1750 µl / min, more preferably 10 to 1500 µl / min, more preferably 20 to 1000 µl / min, and most preferably 50 to 500 µl / min.

[0046] Instead of the diluting liquid, other liquids can also be introduced through the liquid inlet opening. For example, a defined reference solution can be introduced to determine the zero point of a downstream analytical instrument. Alternatively, one or more calibration solutions, i.e., solutions with components of known concentrations, can be introduced to calibrate the instrument and / or the downstream analytical instrument.

[0047] Preferably, the liquid inlet opening for the flow of the liquid sample into the chamber and / or the liquid inlet opening for introducing a diluting liquid into the chamber is located in the lower region of the chamber, more preferably at or near the transition between the upper and lower regions of the chamber.

[0048] Preferably, the chamber further comprises a gas inlet opening for introducing gases into the chamber. The gas inlet opening is preferably located in the upper region of the chamber, more preferably in the upper half of the upper region of the chamber. Preferably, the gas inlet opening is located on the same plane as the gas phase outlet opening; more preferably, the gas inlet opening is located on the same plane as the gas phase outlet opening and is opposite the gas phase outlet opening in the chamber.

[0049] Carrier gas can be introduced into the chamber through the gas inlet opening. The carrier gas is preferably an inert gas such as N₂, Ar, or dried air, particularly preferably N₂. The carrier gas serves to purge the chamber, especially before commissioning, to remove moisture from the chamber.

[0050] Preferably, the chamber further comprises a device for regulating the flow rate of gases into the gas inlet opening for supplying gases into the chamber. The flow rate is preferably 50 ml / min to 1000 ml / min, more preferably 100 ml / min to 900 ml / min, more preferably 200 ml / min to 800 ml / min, and most preferably 300 ml / min to 600 ml / min.

[0051] Preferably, the chamber further comprises a gas outlet opening (11) for the release of carrier gas from the chamber. The carrier gas can escape from the chamber through the gas outlet opening during purging, as described above. The gas outlet opening is preferably located in the upper region of the chamber, more preferably at the same level, i.e., the same height, as the gas inlet opening.

[0052] The gas phase outlet opening for the release of the generated gas phase from the chamber and / or the gas inlet opening for the injection of gases into the chamber and / or the gas outlet opening for the release of carrier gas from the chamber are preferably located in the upper half of the upper region of the chamber, more preferably in the upper third of the upper region of the chamber.

[0053] In a preferred embodiment of the device, the gas phase outlet opening for the release of the generated gas phase from the chamber and the gas inlet opening for the injection of gases into the chamber and the gas outlet opening for the release of carrier gas from the chamber are located in the upper half of the upper region of the chamber, more preferably in the upper third of the upper region of the chamber. Methods for partial transfer

[0054] The present invention further relates to a method for the partial conversion of a liquid sample comprising several components into the gas phase, comprising the steps a) Introducing the multi-component liquid sample into a heated chamber of a device, b) partially converting the liquid sample into the gas phase, so that a gas / liquid two- or multi-phase system is established in the chamber, and c) removing the gas phase of the gas / liquid two- or multi-phase system from the chamber through a gas phase outlet opening of the chamber wherein the chamber (2) has an upper region (2a) and a lower region (2b), wherein the gas phase outlet opening (5) is located in the upper region (2a) of the chamber (2), wherein the lower region (2b) is connected to the upper region (2a), and wherein the upper region (2a) has the shape of a body of revolution with constant diameter and the lower region (2b) has the shape of a body of revolution with decreasing diameter.

[0055] All embodiments of the device according to the invention as described above are also preferred embodiments of the device used in the method according to the invention for the partial conversion of a liquid sample comprising several components into the gas phase.

[0056] In particular, the heated chamber of the method according to the invention is preferably designed as described above in all embodiments of the device. More preferably, a device comprising the heated chamber as described above in all embodiments of the device is used in the method according to the invention for the partial conversion of a liquid sample comprising several components into the gas phase.

[0057] The advantages of the device according to the invention described above apply analogously to the method according to the invention.

[0058] The introduction of the multi-component liquid sample into a heated chamber of the device in step a) is preferably carried out via the liquid inlet opening for the inlet of the liquid sample, as described above.

[0059] The temperature of the liquid sample before introduction in step a) is preferably 20°C to 120°C, more preferably between 25°C and 90°C, and further more preferably between 30°C and 70°C.

[0060] Preferably, the liquid sample is introduced into the chamber in step a) at a flow rate of 1 µl / min to 3000 µl / min, more preferably 2 µl / min to 2000 µl / min, more preferably 5 µl / min to 1750 µl / min, more preferably 10 µl / min to 1500 µl / min, more preferably 20 µl / min to 1000 µl / min, and most preferably 50 µl / min to 500 µl / min. The liquid sample is preferably introduced into the chamber via a device, in particular a spindle valve, as described above. The liquid sample is introduced into the chamber via a liquid inlet opening of the chamber, as described above.

[0061] Preferably, the introduction in step a) is carried out such that at most the entire lower region of the chamber, or at most the entire cavity formed by the lower region of the chamber, is filled with the liquid part or liquid phase of the liquid sample. The lower region of the chamber thus serves to completely contain the liquid sample. The upper region of the chamber, on the other hand, remains free of liquid parts or liquid phases of the liquid sample, but instead only contains the components that have been converted into the gas phase. This prevents liquid parts or liquid phases of the liquid sample from entering the gas phase outlet, and thus also the downstream analytical device. The volume of the liquid sample in the chamber is typically between 10 and 400 µl, preferably between 20 and 350 µl, and more preferably between 30 and 300 µl.Accordingly, the lower part of the chamber, which is preferably shaped as a cone or truncated cone as described above, typically has a volume of 10 to 400 µl, preferably between 20 and 350 µl, more preferably between 30 and 300 µl.

[0062] Preferably, the introduction of the liquid sample in step a) and the extraction of the gas phase in step c) are carried out continuously. This means that both the liquid sample in step a) and the gas phase extraction in step c) are performed without interruption.

[0063] In an alternative embodiment, the introduction of the liquid sample in step a) and the extraction of the gas phase in step c) are time-synchronized. Time-synchronized means that a transfer interval alternates with an interruption interval. During the transfer interval, both the introduction of the liquid sample in step a) and the extraction of the gas phase in step c) take place. During the interruption interval, neither the introduction of the liquid sample in step a) nor the extraction of the gas phase in step c) takes place. The duration of the transfer interval can be the same as the duration of the interruption interval.The duration of the transfer interval is usually 1 second to 60 seconds, preferably 2 seconds to 50 seconds, and most preferably 3 seconds to 40 seconds, and the duration of the interruption interval is usually between 10 seconds and up to 24 hours, more preferably up to 12 hours, more preferably up to 1 hour, more preferably up to 30 minutes, more preferably up to 15 minutes, more preferably up to 5 minutes, and most preferably up to 1 minute.

[0064] The partial conversion in step b) takes place at a temperature that is preferably in the range of 20°C to 300°C, more preferably in the range of 25°C to 275°C, more preferably in the range of 30°C to 250°C, more preferably in the range of 35°C to 225°C, more preferably in the range of 40°C to 200°C, and most preferably in the range of 45°C to 175°C. This temperature prevailing inside the chamber can be set by one or more heating elements as described above.

[0065] Preferably, the gas / liquid two- or multiphase system in the chamber in step b) is at least 90% in equilibrium, more preferably at least 93% in thermodynamic equilibrium, further more preferably at least 96% in thermodynamic equilibrium, and most preferably at least 98% in thermodynamic equilibrium. Equilibrium is defined as the state established by the temperature in the chamber. In other words, at a given temperature, an equilibrium is established after a certain time between the liquid and gaseous phases of each component of the liquid sample in the chamber.

[0066] The establishment of equilibrium in step b) preferably occurs within a time of 0.5 s to 30 s, more preferably within 1 s to 20 s, further more preferably within 2 s to 10 s, and most preferably within 3 s to 8 s. Without being bound by theory, the time required to establish equilibrium in step b) depends not only on the quantity or volume of the liquid sample present in the chamber. With a small quantity or volume of the liquid sample, for example, 10 to 20 µl, equilibrium is generally established in step b) within a short time, as described above. However, the time also depends on the temperature difference of the liquid sample, specifically between the temperature of the liquid sample before it is introduced into the chamber and the desired temperature to which the liquid sample is to be brought in the chamber, as described above.The greater this temperature difference, the longer it usually takes to reach equilibrium. For example, if the liquid sample is introduced into the chamber at a temperature of 20°C, and the desired temperature is 30°C, the small temperature difference means that equilibrium is usually reached in the chamber within a short time, as described above.

[0067] Preferably, the gas phase is withdrawn from the chamber in step c) at a flow rate of 10 ml / min to 500 ml / min, more preferably from 20 ml / min to 450 ml / min, more preferably from 40 ml / min to 400 ml / min, more preferably from 60 ml / min to 300 ml / min, and most preferably from 100 ml / min to 200 ml / min. The gas phase is withdrawn from the chamber via a gas phase outlet opening in the chamber, as described above.

[0068] Preferably, the liquid phase of the gas / liquid two- or multi-phase system is removed from the chamber through a liquid drain opening, as described above. Removal can be carried out, for example, by a pump, as described above. Online procedure

[0069] One embodiment relates to a method for the online determination and analysis of components of a liquid sample comprising multiple components, wherein a method for the partial conversion of a liquid sample comprising multiple components into the gas phase, as in all embodiments as described above, is used, wherein the liquid sample comprising multiple components is taken from a process which is upstream of step a) or from a container which is upstream of step a), and wherein the gas phase taken in step c) is introduced into a downstream analysis device.

[0070] All embodiments of the device according to the invention, as described above in all embodiments, are also preferred embodiments of the device used in the method according to the invention for the online determination and analysis of components of a liquid sample comprising several components.

[0071] In particular, the heated chamber of the method according to the invention is preferably designed as described above in all embodiments of the device. More preferably, a device comprising the heated chamber as described above in all embodiments of the device is used in the method according to the invention for the online determination and analysis of components of a liquid sample comprising several components.

[0072] All embodiments of the method for the partial conversion of a multi-component liquid sample into the gas phase as described above are also preferred embodiments of the method for the online determination and analysis of components of a multi-component liquid sample.

[0073] The advantages of the device and method according to the invention described above for the partial conversion of a liquid sample comprising several components into the gas phase apply analogously to the method according to the invention for the online determination and analysis of components of a liquid sample comprising several components.

[0074] The multi-component liquid sample is taken from a process or container that precedes step a). The multi-component liquid sample can, for example, be taken from a reactor, a pipeline, or a container within the process.

[0075] Preferably, step a) is an upstream process or the container connected to the device by means of a fluid connection. The fluid connection preferably comprises a pipe, a hose, a capillary or combinations thereof.

[0076] Preferably, step a) upstream process comprises a dilution process, more preferably an oil dilution process, in particular a motor oil dilution process, a solvent recovery process, a pharmaceutical process, or a wastewater process. More preferably, step a) upstream process is a dilution process, more preferably an oil dilution process, in particular a motor oil dilution process, a solvent recovery process, a pharmaceutical process, or a wastewater process.

[0077] A pharmaceutical process is, for example, a process for manufacturing medicines, especially liquid medicines.

[0078] Preferably, the ratio of the volume of the liquid phase of the liquid sample to the gaseous phase of the liquid sample after setting equilibrium in step b), and after optional dilution with diluting liquid and / or (carrier) gases as described above, in the chamber is 1:150, more preferably 1:100.

[0079] The extracted gas phase from step c) is introduced into a downstream analysis device. This device is preferably connected to the downstream analysis device via a fluid connection. The fluid connection preferably comprises a tube, a hose, a capillary, or a combination thereof. The measurement time in the downstream analysis device for analyzing and determining the components contained in the extracted gas phase is typically 0.05 to 30 seconds, preferably 0.1 to 15 seconds.

[0080] Preferably, the downstream analytical device is a mass spectrometer, as described above. In the mass spectrometer, all components present in the gas phase extracted in step c) can be qualitatively and quantitatively determined.

[0081] Average residence time within the meaning of this application refers to the time that the minor component(s) of the liquid sample require on average or on average from a specific first point or first step, for example from the removal of the liquid sample from the process preceding step a), to a specific second point or second step, for example from the introduction into the analytical device following step c).

[0082] Preferably, the average residence time of the components contained in the liquid sample between the removal of the liquid sample from the process upstream of step a) and the introduction into the analytical device downstream of step c) is a maximum of 5 minutes, more preferably a maximum of 3 minutes and most preferably a maximum of 1 minute.

[0083] Preferably, the molecular weight of each component transferred into the gas phase is a maximum of 500 Daltons, more preferably a maximum of 450 Daltons, and further more preferably a maximum of 400 Daltons. Components with a molecular weight of more than 500 Daltons are typically not transferred into the gas phase at the temperatures used in the process according to the invention, or only in concentrations that are not measurable. The concentration of each component transferred into the gas phase is preferably between 1 ppb and 1000 ppb, more preferably between 5 ppb and 750 ppb, and most preferably between 10 ppb and 500 ppb.

[0084] In this application, ppb means "parts per billion", that is 10 -9< .

[0085] Preferably, the temperature of the extracted gas phase after step c) does not fall below the dew point of the components present in the gas phase. Thus, none of the components present in the gas phase condense into their liquid state; instead, the components reach the downstream analytical device in their gaseous state. This temperature drop can be prevented, for example, by thermal insulation and / or heating of the fluid connection between the device and the downstream analytical device.

[0086] Preferably, the average residence time between introducing the liquid sample into the chamber in step a) and removing the gas phase of the gas / liquid two- or multi-phase system from the chamber in step c) is a maximum of 1 minute, more preferably a maximum of 45 seconds, and most preferably a maximum of 30 seconds. The average residence time is defined as above.

[0087] The multi-component liquid sample preferably comprises a main component and one or more minor components. The main component is in a liquid state before the liquid sample is introduced into the chamber of the device. The main component preferably comprises lubricating oil, motor oil, wastewater, solvents, and mixtures thereof.

[0088] The one or more minor components are preferably present in the liquid sample in a liquid state before the liquid sample is introduced into the chamber of the device, or in a gaseous state and thereby dissolved in the liquid main component.

[0089] The secondary component preferably comprises acetic acid, acetone, acetonitrile, anisole, benzene, 1-butanol, 2-butanol, butyl acetate, tert-butyl methyl ether, tetrachloromethane, chlorobenzene, trichloromethane, isopropylbenzene, cyclohexane, 1,2-dichloroethane, 1,1-dichloroethene, 1,2-dichloroethene, dichloromethane, 1,2-dimethoxyethane, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 1,3-dioxane, ethanol, 2-ethoxyethanol, ethyl acetate, ethylene glycol, ethyl ether, ethyl formate, methanamide, methanoic acid, heptane, hexane, isobutyl acetate, isopropyl acetate, methanol, 2-methoxyethanol, methyl acetate, 3-methyl-1-butanol, methyl butyl ketone, methylcyclohexane, and methyl ethyl ketone. Methyl isobutyl ketone, 2-methyl-1-propanol, N-methylpyrrolidone, nitromethane, pentane, T1-pentanol, 1-propanol, 2-propanol, propyl acetate, pyridine, sulfolane, tetrahydrofuran, tetralin, toluene, 1,1,1-trichloroethane, 1,1,2-trichloroethene, triethylamine, xylene, butane, cyclopentane, octene or mixtures thereof.

[0090] The concentration of the main component in the liquid sample is preferably 85 wt.% or more, and the sum of all minor components in the liquid sample is 15 wt.% or less. More preferably, the concentration of the main component in the liquid sample is 90% or more, and the sum of all minor components in the liquid sample is 10 wt.% or less. More preferably, the concentration of the main component in the liquid sample is 92.5 wt.% or more, and the sum of all minor components in the liquid sample is 7.5 wt.% or less. More preferably, the concentration of the main component in the liquid sample is 95 wt.% or more, and the sum of all minor components in the liquid sample is 5 wt.% or less. Most preferably, the concentration of the main component in the liquid sample is 97.5% or more, and the sum of all minor components in the liquid sample is 2.5 wt.% or less.% or less.

[0091] The concentrations mentioned above always refer to the concentrations of the main and minor component(s) in the liquid sample present in the chamber, after the optional introduction of a diluting liquid and / or the optional injection of gases into the chamber, as described above. If the concentration of the minor components to be detected exceeds 15 wt.% in the liquid sample in the chamber, inaccuracies may arise in the quantitative determination of these minor components in a downstream analytical device, for example, due to nonlinearities. To remedy this, a diluting liquid can be introduced into the chamber through the additional liquid inlet port using a flow rate control device, as described above. The diluting liquid is used to dilute the liquid sample in the chamber and is preferably the "zero liquid" or...The main component of the liquid sample in the chamber, as described above. This reduces the concentration of the minor components to be detected in the liquid sample to 15 wt.% or less, thus avoiding problems in the quantitative determination of these minor components. use

[0092] The invention further relates to the use of the device according to the invention, as described above in all embodiments, as a sample preparation device in a method for the partial conversion of a liquid sample comprising several components into the gas phase, as described above in all embodiments.

[0093] One embodiment relates to the use of the device according to the invention, as described above in all embodiments, as a sample preparation device in a method for the online determination and analysis of components of a liquid sample comprising several components, as described above in all embodiments.

[0094] Further details, features and advantages of the subject matter of the invention will become apparent from the following description of the accompanying figures, in which exemplary preferred embodiments of the invention are shown.

[0095] This shows Figure 1 a top view of an embodiment of the device according to the invention for the partial conversion of a liquid sample comprising several components into the gas phase, Figure 2 a section through the device according to the invention along line AA in Figure 1 , Figure 3a section through the device according to the invention along line BB in Figure 1 . Figure 4 a section through the device according to the invention along line CC in Figure 2 , Figure 5 a measurement result of an online measurement of fuel dilution according to an embodiment of the inventive method, and Figure 6 a measurement result of an online monitoring of a fermentation process according to an embodiment of the inventive method.

[0096] Figure 1Figure 1 shows a top view of an embodiment of the device (1) according to the invention for the partial conversion of a liquid sample comprising several components into the gas phase. On the right side of the device (1) are arranged the device (8) for controlling the flow rate of the liquid sample into the liquid inlet opening (3) and the device (9) for controlling the flow rate of the diluting liquid into the liquid inlet opening (6). In this embodiment, both devices (8, 9) are designed as spindle valves, with which the flow of the liquid sample or the diluting liquid into the chamber (2) can be controlled.

[0097] On the side of the device opposite the devices (8,9) an outlet for carrier gas is arranged.

[0098] A section through the device according to the invention along line AA in Figure 1 is in Figure 2The chamber (2) arranged inside the device (1) has an upper region (2a) and a lower region (2b) adjoining the upper region (2a). The upper region (2a) has the shape of a right circular cylinder, while the lower region (2b) has the shape of a right cone, with the liquid drain opening (4) located at the apex of the cone. The diameter of the circular cylinder corresponds to the diameter of the circular base of the cone.

[0099] A heating element (10) is located above the upper area (2a) of the chamber (2) and heats the chamber via the walls bounding the chamber, in particular those walls bounding the upper area (2a) of the chamber (2), such that the desired temperature is established inside the chamber (2).

[0100] In the upper region (2a), the chamber (2) has a gas inlet opening (7) for supplying gases into the chamber (2), and the gas phase outlet opening (5) opposite the opening (7). The gas phase outlet opening (5) is as shown in Figure 2 shown connected to a capillary, which in turn can be connected to an analysis device (not shown). As shown Figure 2Furthermore, it can be seen that both opening (7) and opening (5) are located at the same level in the upper region (2a) of the chamber (2). The chamber (2) also has a liquid inlet opening (3) for the liquid sample to flow into the chamber (2) and a liquid inlet opening (6) for introducing a diluting liquid into the chamber (2). Both liquid inlet openings (3, 6) are located at the transition between the upper region (2a) and the lower region (2b) of the chamber (2). The lower region (2b) of the chamber (2) is filled with the liquid sample or the diluting liquid via these two liquid inlet openings (3, 6).

[0101] Figure 3 shows a section through the device according to the invention along line BB in Figure 1The gas outlet opening (11) for the release of carrier gas from the chamber (2) is located at the same level in the upper region (2a) of the chamber (2) as the gas phase outlet opening (5) for the release of the generated gas phase from the chamber (2). The liquid drain opening (4) for the discharge of liquid components not converted into the gas phase is located, as already described in Figure 2 shown, at the top of the cone of the lower region (2b). Figure 3 also shows the liquid inlet opening (3) and the spindle valve (8) associated with this inlet opening.

[0102] Figure 4 shows a section through the device according to the invention along line CC in Figure 2 . In Figure 4 It can be seen that in this embodiment the chamber (2) is arranged centrally in the device (1). As already mentioned in Figures 2 and 3 shown, also shows Figure 4that the liquid drain opening (4) is located centrally at the bottom of the chamber (2). In Figure 4 The liquid inlet openings (3, 6) with their associated valves (8, 9) can also be seen. Example 1

[0103] Example 1 relates to the fuel dilution of engine oil and is intended to illustrate, by way of example, the principle of the inventive method for the online determination and analysis of components of a liquid sample comprising several components. Here, a device (1) according to the embodiment described above, as well as in Figures 1 to 4 As shown, an ion-molecule reaction mass spectrometer (IMR-MS; commercially available from V&F Analyse- und Messtechnik GmbH) was used to determine the components of the liquid sample to be transferred into the gas phase. The liquid sample to be analyzed was taken from a motor oil mixture of 20 ml diesel in 5 liters of motor oil. Figure 5The concentration profile of typical diesel hydrocarbons "TS1" to "TS6" over time is shown. TS1 to TS6 are long-chain, i.e., C12 to C16, hydrocarbons of diesel fuel. (Referring to...) Figure 5 At second 23, 100 µl of the liquid sample are introduced into the chamber (2) of the device (1) via the liquid inlet opening (3) using the spindle valve (8). Heating the liquid sample in the chamber (2) from 40°C to 130°C takes approximately 1 minute. Subsequently, the components of the liquid sample that have transitioned into the gas phase are transferred through the gas phase outlet opening (5) of the device (1) via a capillary into the mass spectrometer for determination and analysis of the gaseous components. This process takes approximately 1 minute 21 seconds to 3 minutes 50 seconds. Figure 5The mass spectrometer measures the concentrations of the gaseous components. After the measurement is complete, the remaining engine oil in chamber (2) is pumped out of chamber (2) through the liquid drain opening (4) by a peristaltic pump. Example 2

[0104] Example 2 illustrates a further application example of the inventive method for the online determination and analysis of components of a liquid sample comprising several components. The method can not only be used for the determination and analysis of components, but can also serve as a process monitoring system or process monitoring method. Online process monitoring is illustrated using a maize fermentation process as an example; see [reference]. Figure 6Example 2 uses the same apparatus (1) including the mass spectrometer as in Example 1, with liquid samples from a fermentation process being continuously introduced from the fermenter into the apparatus (1). The measured components F1 to F4, which are transferred into the gas phase by means of the apparatus (1), are Figure 6 These are characteristic compounds of the fermentation process that indicate the proper functioning of the system or the fermentation process itself. Up to approximately 2 hours and 30 seconds in Figure 6 The fermentation process being monitored proceeds normally. Subsequently, significant fluctuations in the concentration of these characteristic components in the gas phase are detected, indicating a disturbance in the process.

[0105] The two examples above are intended to demonstrate that the device and method according to the invention are suitable for online determination and analysis of components and for monitoring continuous processes online, i.e., in "real time". In other words, disturbances in the processes to be monitored can be detected and diagnosed within a very short time, i.e., within a few minutes. Reference symbol list

[0106] 1 Device for the partial conversion of a liquid sample comprising several components into the gas phase, 2 heated chamber, 2a upper part of the chamber (2), 2b lower part of the chamber (2), 3 Liquid inlet opening for the inflow of the liquid sample into the chamber (2), 4 Liquid drain opening for the drainage of liquid components not converted into the gas phase from the chamber (2), 5Gas phase outlet opening for the release of the generated gas phase from the chamber (2), 6 Liquid inlet opening for introducing a diluting liquid into the chamber (2), 7 Gas inlet opening for feeding gases into the chamber (2), 8 Device for controlling the flow rate of the liquid sample into the liquid inlet opening (3), 9 Device for controlling the flow rate of the diluting liquid into the liquid inlet opening (6), 10 Heating element 11 Gas outlet opening for the release of carrier gas from the chamber (2)

Claims

1. A device (1) for partially transitioning a liquid sample comprising a plurality of components into the gas phase, said device comprising (a) a heatable chamber (2) in which a two-phase or multi-phase gas / liquid system is generated, said chamber having (a1) a liquid inflow opening (3) for inflow of the liquid sample, (a2) a liquid outflow opening (4) for outflow from the chamber (2) of liquid remnants not transitioned into the gas phase, and (a3) a gas phase discharge opening (5) for discharging the generated gas phase out of the chamber, and (b) a device (6) for controlling the flow rate of the liquid sample into the liquid inflow opening (3) from 1 µl / min to 3000 µl / min, the chamber (2) having an upper region (2a) and a lower region (2b), the gas phase discharge opening (5) being present in the upper region (2a) of the chamber (2), the lower region (2b) being connected to the upper region (2a), characterized in that the upper region (2a) has the shape of a rotation body having a constant diameter and the lower region (2b) has the shape of a rotation body having a decreasing diameter.

2. The device according to any one of the preceding claims, wherein the chamber (2) has a volume from 0.1 to 25 cm3.

3. The device according to any one of the preceding claims, wherein the device (1) further comprises a device for controlling the gas phase flow out of the chamber (2) from 10 ml / min to 500 ml / min.

4. The device according to any one of the preceding claims, wherein the device (1) further comprises a heating element (10) and the chamber (2) is heated by means of the walls bounding the chamber (2).

5. The device according to any one of the preceding claims, wherein the chamber (2) comprises a further liquid inflow opening (6) for introducing a diluting liquid, and / or wherein the chamber (2) further comprises a gas entry opening (7) for feeding carrier gases into the chamber (2) and / or a gas discharge opening (11) for discharging carrier gas out of the chamber (2).

6. A method for partially transitioning a liquid sample comprising a plurality of components into the gas phase, comprising the steps of a) introducing the liquid sample comprising a plurality of components into a heatable chamber (2) of a device (1), b) partially transitioning the liquid sample into the gas phase, so that a two-phase or multi-phase gas / liquid system arises in the chamber (2), c) removing the gas phase of the two-phase or multi-phase gas / liquid system from the chamber (2) through a gas phase discharge opening (5) of the chamber (2), the chamber (2) having an upper region (2a) and a lower region (2b), the gas phase discharge opening (5) being present in the upper region (2a) of the chamber (2), the lower region (2b) being connected to the upper region (2a), characterized in that the upper region (2a) has the shape of a rotation body having a constant diameter and the lower region (2b) has the shape of a rotation body having a decreasing diameter.

7. The method according to claim 6, wherein the partial transitioning in step b) takes place at a temperature in a range between 20°C and 300°C.

8. A method for identifying and analyzing components of a liquid sample comprising a plurality of components online, wherein a method according to claims 6 through 7 is used, wherein the liquid sample comprising a plurality of components is taken from a process upstream of step a) or from a container upstream of step a), and wherein the gas phase removed in step c) is introduced into an analysis device connected downstream.

9. The method according to claim 8, wherein the analysis device connected downstream is a mass spectrometer.

10. The method according to any one of the claims 8 through 9, the chamber (2) having an upper region (2a) and a lower region (2b), the lower region (2b) being connected to the upper region (2a), and wherein the upper region (2a) has the shape of a rotation body having a constant diameter and the lower region (2b) has the shape of a rotation body having a decreasing diameter, and wherein the introducing in step a) is performed such that no more than the lower region (2b) of the chamber (2) is filled with the liquid phase of the liquid sample.

11. The method according to any one of the claims 8 through 10, wherein the average dwell time of the components present in the liquid sample between removing the liquid sample from the process upstream of step a) and introducing into the analysis device connected downstream of step c) is no greater than 5 minutes.

12. The method according to any one of the claims 8 through 11, wherein the molecular weight of each of the components transitioned into the gas phase in step b) is no greater than 500 daltons.

13. The method according to any one of the claims 8 through 12, wherein the concentration in the gas phase in the chamber (2) of each of the components transitioned into the gas phase in step b) is between 1 ppb and 1000 ppb.

14. The method according to any one of the claims 8 through 13, wherein the liquid sample comprising a plurality of components comprises a primary component and one or more secondary components, wherein the concentration of the primary component in the liquid sample is 90% by weight or greater, and the sum of all secondary components in the liquid sample is 10% by weight or less.

15. The method according to any one of the claims 6 through 14, wherein a device (1) according to any one of the claims 1 through 5 is used.

16. A use of a device according to any one of the claims 1 through 5 as a sample preparation device in a method according to any one of the claims 6 through 15.