DEVICE AND METHOD FOR PARTIAL TRANSFER OF A LIQUID SAMPLE, COMPRISING MULTIPLE COMPONENTS AND METHOD FOR THE ONLINE DETERMINATION AND ANALYSIS OF THESE COMPONENTS

Abstract

The invention relates to a device and method for partial conversion of a fluid sample comprising a plurality of components and a process for on-line determination and analysis of components of a fluid sample comprising a plurality of components. The invention also relates to the use of the device as a sample treatment device.

Claims

1. Device (1) for the partial conversion of a liquid sample comprising a plurality of components to the gas phase, comprising: (a) a heatable chamber (2) in which a two-phase or multi-phase gas/liquid system is produced, having (a1) a liquid inlet port (3) for the supply of the liquid sample, (a2) a liquid outlet port (4) for the discharge of liquid components from the chamber (2) which have not been converted to the gas phase, and (a3) a gas phase outlet port (5) for the discharge of the generated gas phase from the chamber; and (b) a device (6) for controlling the flow rate of the liquid sample into the liquid inlet port (3) from 1 l/min to 3000 l/min, characterised in that the chamber (2) has an upper region (2a) and a lower region (2b), the gas phase outlet port (5) being located in the upper region (2a) of the chamber (2).

2. Device according to claim 1, wherein the chamber (2) has an upper region (2a) and a lower region (2b), wherein the lower region (2b) is connected to the upper region (2a), and wherein the upper region (2a) is in the shape of a solid of revolution of constant diameter and the lower region (2b) is in the shape of a solid of revolution of decreasing diameter.

3. Device according to claim 1, wherein the chamber (2) has a volume of 0.1 to 25 cm.sup.3.

4. Device according to claim 1, the device (1) further comprising a device for controlling the gas phase flow from the chamber (2) from 10 ml/min to 500 ml/min.

5. Device according to claim 1, the device (1) further comprising a heating element (10), wherein heating of the chamber (2) is effected via the walls delimiting the chamber (2).

6. Device according to claim 1, wherein the chamber (2) comprises a further liquid inlet port (6) for inserting a diluent liquid, and/or wherein the chamber (2) further comprises a gas inlet port (7) for feeding carrier gases into the chamber (2) and/or a gas outlet port (11) for the discharge carrier gas from the chamber (2).

7. Method for the partial gas phase conversion of a liquid sample comprising a plurality of components, 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 converting the liquid sample to the gas phase so that a gas/liquid two-phase or multi-phase system is created in the chamber (2), c) extracting the gas phase of the gas/liquid two-phase or multi-phase system from the chamber (2) through a gas phase outlet port (5) of the chamber (2), characterised in that the chamber (2) has an upper region (2a) and a lower region (2b), wherein the gas phase outlet port (5) is located in the upper region (2a) of the chamber (2).

8. Method according to claim 7, wherein the partial conversion in step b) is effected at a temperature which is in a range between 20 C. and 300 C.

9. Method according to claim 8, wherein the gas/liquid two-phase or multi-phase system in the chamber in step b) is at least 90% in the equilibrium state and/or wherein creating the equilibrium state in step b) takes between 0.5 seconds to 30 seconds.

10. Method for on-line determination and analysis of components of a fluid sample comprising a plurality of components using a method according to claim 7.

11. Method according to claim 10, wherein the liquid sample comprising a plurality of components is extracted from a process upstream of step a) or from a container upstream of step a).

12. Method according to claim 10, wherein the gas phase extracted in step c) is introduced into a downstream analysis device.

13. Method according to claim 10, wherein the downstream analysis device is a mass spectrometer.

14. Method according to claim 10, wherein the chamber (2) has an upper region (2a) and a lower region (2b), wherein the lower region (2b) is connected to the upper region (2a), and wherein the upper region (2a) is in the shape of a solid of revolution of constant diameter and the lower region (2b) is in the form of a solid of revolution of decreasing diameter, and wherein the introducing in step a) is carried out such that, at most, the lower region (2b) of the chamber (2) is filled with the liquid phase of the liquid sample.

15. Method according to claim 11, wherein the average residence time of the components contained in the liquid sample between extracting the liquid sample from the process upstream of step a) and introducing into the analysis device downstream of step c) is a maximum of 5 minutes.

16. Method according to claim 11, wherein the molecular weight of any of the components converted to the gas phase in step b) is a maximum of 500 Daltons.

17. Method according to claim 11, wherein the concentration of the components converted to the gas phase in step b) is between 1 ppb and 1000 ppb, respectively, in the gas phase in the chamber (2).

18. Method according to claim 11, wherein the liquid sample comprising a plurality of components comprises a main component and one or several secondary components, wherein the concentration of the main component in the liquid sample is 90 wt. % or more, and the sum of all secondary components in the liquid sample is 10 wt. % or less.

19. Method according to claim 7, wherein a device (1) according to claim 1 is used.

20. Method for the partial gas phase conversion of a liquid sample comprising a plurality of components, comprising the steps of a) introducing the liquid sample comprising a plurality of components into a heatable chamber (2) of a device (1), comprising: (a) a heatable chamber (2) in which a two-phase or multi-phase gas/liquid system is produced, having (a1) a liquid inlet port (3) for the supply of the liquid sample, (a2) a liquid outlet port (4) for the discharge of liquid components from the chamber (2) which have not been converted to the gas phase, and (a3) a gas phase outlet port (5) for the discharge of the generated gas phase from the chamber; and (b) a device (6) for controlling the flow rate of the liquid sample into the liquid inlet port (3) from 1 l/min to 3000 l/min, b) partially converting the liquid sample to the gas phase so that a gas/liquid two-phase or multi-phase system is created in the chamber (2), c) extracting the gas phase of the gas/liquid two-phase or multi-phase system from the chamber (2) through a gas phase outlet port (5) of the chamber (2).

Description

[0104] Further details, features and advantages of the subject-matter of the invention can be understood from the following description of the appendant figures, in which the preferred embodiments of the invention are illustrated.

[0105] Shown are:

[0106] FIG. 1 an plan view of an embodiment of the device according to the invention for the partial conversion of a liquid sample comprising a plurality of components to the gas phase,

[0107] FIG. 2 a cross-section through the device according to the invention along the line A-A in FIG. 1,

[0108] FIG. 3 a cross-section through the device according to the invention along the line B-B in FIG. 1,

[0109] FIG. 4 a cross-section through the device according to the invention along the line C-C in FIG. 2,

[0110] FIG. 5 a measurement result of an on-line measurement of fuel dilution according to an embodiment of the method according to the invention, and

[0111] FIG. 6 a measurement result of an on-line monitoring of a fermentation process according to an embodiment of the method according to the invention.

[0112] FIG. 1 shows a plan view of an embodiment of the device (1) according to the invention for the partial conversion of a liquid sample comprising a plurality of components to the gas phase. On the right side of the device (1), the device (8) for controlling the flow rate of the liquid sample into the liquid inlet port (3) and the device (9) for controlling the flow rate of the diluent liquid into the liquid inlet port (6) are arranged. In this exemplary embodiment, both devices (8, 9) are designed as spindle valves, by means of which the flow of the liquid sample or the diluent liquid into the chamber (2) can be controlled.

[0113] An outlet for carrier gas is arranged on the side of the device opposite the devices (8, 9).

[0114] A cross-section through the device according to the invention along the line A-A in FIG. 1 is shown in FIG. 2. The chamber (2) located inside the device (1) has an upper region (2a) and a lower region (2b) adjacent to the upper region (2a). The upper region (2a) has the shape of a straight circular cylinder, while the lower region (2b) has the shape of a straight cone, the liquid outlet port (4) being located at the tip of the cone. The diameter of the circular cylinder corresponds to the diameter of the circular base of the cone.

[0115] A heating element (10) is located above the upper region (2a) of the chamber (2) and heats the chamber via the walls delimiting the chamber, in particular those walls delimiting the upper region (2a) of the chamber (2), in such a way that the desired temperature is reached inside the chamber (2).

[0116] In the upper region (2a), the chamber (2) has a gas inlet port (7) for feeding gases into the chamber (2), and the gas phase outlet port (5) opposite the port (7). The gas phase outlet port (5) is connected to a capillary, as shown in FIG. 2, which in turn can be connected to an analysis device (not shown). As can also be seen from FIG. 2, both the port (7) and the port (5) are at the same height in the upper region (2a) of the chamber (2). The chamber (2) further has a liquid inlet port (3) for the inlet of the liquid sample into the chamber (2) and a liquid inlet port (6) for the introduction of a diluent liquid into the chamber (2). Both liquid inlet ports (3, 6) are arranged at the transition between the upper region (2a) and the lower region (2b) of the chamber (2). These two liquid inlet ports (3, 6) are used to fill the lower region (2b) of the chamber (2) with liquid sample or diluent liquid.

[0117] FIG. 3 shows a cross-section through the device according to the invention along the line B-B in FIG. 1. The gas outlet port (11) for the outlet of carrier gas from the chamber (2) is located at the same height in the upper region (2a) of the chamber (2) as the gas phase outlet port (5) for the outlet of the generated gas phase from the chamber (2). As already shown in FIG. 2, the liquid outlet port (4) for the discharge of liquid components not converted to the gas phase is located at the tip of the cone of the lower region (2b). FIG. 3 also shows the liquid inlet port (3) and the spindle valve (8) assigned to this inlet port.

[0118] FIG. 4 shows a cross-section through the device according to the invention along the line C-C in FIG. 2. In FIG. 4, it can be seen that the chamber (2) in this embodiment is arranged centrally in the device (1). As already shown in FIGS. 2 and 3, FIG. 4 also shows that the liquid outlet port (4) is centered at the bottom of the chamber (2). In FIG. 4, the liquid inlet ports (3, 6) with their associated valves (8, 9) can also be seen.

Example 1

[0119] Example 1 relates to the fuel dilution of engine oil and is provided to illustrate the principle of the method according to the invention for the on-line determination and analysis of components of a fluid sample comprising a plurality of components. Here, a device (1) according to the above example is used, as shown in FIGS. 1 to 4. An ion-molecule reaction mass spectrometer (IMR-MS; commercially available from V&F Analyse- and Messtechnik GmbH) is used for the determination of the components of the liquid sample to be converted to the gas phase. The liquid sample to be analysed is taken from an engine oil mixture of 20 ml diesel in 5 litres engine oil. In FIG. 5, the concentration curve of typical diesel hydrocarbons TS1 to TS6 over time is illustrated. TS1 to TS6 are long-chain, i.e. C12 to C16 hydrocarbons of diesel fuel. With reference to FIG. 5, at second 23 100 l of the liquid sample is introduced into the chamber (2) of the device (1) via the liquid inlet port (3) with the spindle valve (8). Heating the liquid sample introduced into the chamber (2) from 40 C. to 130 C. takes about 1 minute. Subsequently, the components of the liquid sample which have been converted to the gas phase are transferred through the gas phase outlet port (5) of the device (1) by means of a capillary to the mass spectrometer for the determination and analysis of the gaseous components. The concentrations of the gaseous components are measured in the mass spectrometer from approx. 1 min 21 sec to 3 min 50 sec in FIG. 5. After the end of the measurement, the engine oil remaining in the chamber (2) is pumped out of the chamber (2) through the liquid outlet port (4) by a peristaltic pump.

Example 2

[0120] Example 2 is another application example of the method according to the invention for on-line determination and analysis of components of a fluid sample comprising a plurality of components. The method can not only be used for the determination and analysis of components, but it can also serve as a process monitoring system or process monitoring method. The on-line process monitoring is illustrated with the help of a fermentation process of maize, see FIG. 6. In example 2, the same device (1) including the mass spectrometer as in example 1 is used, wherein liquid samples of a fermentation process from the fermenter are continuously introduced into the device (1). The measured components F1 to F4 in FIG. 6, which are converted to the gas phase by means of a device (1), are characteristic compounds of the fermentation process that indicate the correct functioning of the plant or the fermentation process. Up to approx. 2 h 30 sec in FIG. 6, the fermentation process to be monitored runs normally. Subsequently, considerable fluctuations in the concentration of these characteristic components in the gas phase are detected, which indicates a disturbance in the process.

[0121] The two examples above are intended to demonstrate that the device according to the invention and the method according to the invention for on-line determination and analysis of components are suitable for monitoring continuous processes on-line, 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.

LIST OF REFERENCE SIGNS

[0122] 1 device for the partial conversion of a liquid sample comprising a so plurality of components to the gas phase, [0123] 2 heatable chamber, [0124] 2a upper region of the chamber (2), [0125] 2b lower region of the chamber (2), [0126] 3 liquid inlet port for the inlet of the liquid sample into the chamber (2), [0127] 4 liquid outlet port for the discharge of liquid components from the chamber (2) which have not been converted to the gas phase, [0128] 5 gas phase outlet port for the outlet of the generated gas phase from the chamber (2), [0129] 6 liquid inlet port for introducing a diluent liquid into the chamber (2), [0130] 7 gas inlet port for feeding gases into the chamber (2), [0131] 8 device for controlling the flow rate of the liquid sample into the liquid inlet port (3), [0132] 9 device for controlling the flow rate of the diluent liquid into the liquid inlet port (6), [0133] 10 heating element, [0134] 11 gas outlet port for the outlet of carrier gas from the chamber (2)