DE2118539A1 - Method and device for the analysis of liquid mixtures - Google Patents

Description

See method and device for the analysis of liquid it sgeini

The Erfindun _o relates to the analysis of iron liquid mixtures, and in particular an ancestor and a device for analyzing .Kohlenwasserstoff (KW) mixtures.

In laboratories and chemical engineering it is often necessary to determine the concentration of the constituents of liquid mixtures by analysis. This is particularly important in the case of computer-controlled control and optimization of continuous processes in petroleum processing, where the profitability of a process often depends on precise knowledge of the composition of the liquid mixture to be processed. ¹ or the concentration of certain components of the same.

Because the physical properties of their constituents are similar, certain liquid mixtures can be -in «special the KW *, only difficult to analyze or separate. The components of liquid mixtures can be have similar boiling points and adsorption characteristics “Eggs are composed of similarly non-polar molecules.

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BATH ORIGINAL

Such similarities make the analysis or separation " these liquid mixtures by currently known Methods like chromatography or fractionation are extremely difficult.

An example of a difficult to analyze mixture was given in catalytic reforming to improve the Fuel octane ratings found. Here the feed usually contains a mixture of aromatics, ITaphthenes and paraffins. Both naphthenes and paraffins can be distinguished from aromatics by chromatographic analysis. Because of the similarity of their physical properties however, it is not so easy to distinguish the naphthenes from the paraffins. With the help of a mass spectrometer Such a mixture could indeed be analyzed. Unfortunately, this method works in its current form State of development not to continuously monitor a continuous process. Furthermore, the application the chromatographic analysis commonly used up to now is unsatisfactory because the liquid constituents are similar physical properties are not sufficiently different.

For the automatic control of the catalytic reforming process by means of a computer system, it is important to continuously monitor the haphthene content of the feed to measure, since the naphthenes are the main reactants in the process represent. The naphtha content of the charge is therefore a main or key variable of the process. So if you put this value on a computer, the other influencing variables controls the process, inputs continuously, so the process can be optimized and the yield and quality of the product to enhance.

The invention now enables the solution described; and related problems and provides a method and apparatus by which a characteristic of a liquid;

2 0 9-844 / 0460- <■ ·

BATH ORIGINAL

keite-mixed, like the naphthene eh tilt a KVWIi s clmng continuously measured and monitored by the liquid genxKch subjected to a chemical reaction and a stand- ■ partly at least ο partly converted, chge-separated from the mixture and it is demonstrated in a display device «In one Another embodiment includes the apparatus of the invention a computer coupled to the detector or display device and calculates the concentration of the constituent of interest in the liquid mixture.

The method of the invention basically consists in that the liquid mixture of the chemical reaction mentioned exposed and measured dex * constituent of interest. In a modification of this method, several Components of the mixture through the chemical reaction in another component of the mixture is converted and this component is not subjected to the reaction in one Sample of the Ai-.ggangmixture determined, and it is finally based on an ex · predetermined relationship between the detected components in the unreacted Sample, the reacted sample and the concentration of the active ingredient in the puffiness mixture a signa] generated for this concentration value.

The invention relates to a method for analyzing Liquid mixtures, especially hydrocarbons, the Contain at least two components, of which the first component is based on its physical properties difficult and the second constituent is more easily separated from the liquid mixture due to its physical properties distinguish, characterized in that one

a) the concentration of the second component in one Sample of the liquid mixture determined,

BATH ORIGINAL

2098U / CK66

to) Take a sample of the liquid quality of a chemical Subjects to reaction by which the first constituent of the mixture is at least partially converted into the second constituent is converted ",

c) after this reaction, the concentration of the second component in the sample of the liquid mixture is determined and

d) from the concentrations measured according to a) and c) based on a predetermined relationship between the measured levels of the second component and the Concentration of the same constituents in a comparison sample of a comparison mixture a first signal generated for the concentration of the first component in the liquid mixture.

The invention also relates to a device for carrying out this method by

a) one through which the liquid mixture flows, with a Catalyst-filled reactor chamber door the conversion of the first component of the liquid mixture into the second component,

b) one connected to the inlet end of the reactor anchors Source of the carrier gas that conveys the liquid mixture through the chamber,

c) a heating device connected to the chamber, and

d) a gas chromatography room and a detector, both connected to the outlet of the canine and arranged to determine the concentration of the harvested component in the liquid mixture by measuring the converted proportion of this first component.

2 0 9 8 4 4/0466 BAD ORIGINAL

The invention is to be explained in more detail with reference to the drawing xtferden, in the

Figure 1 is a flow diagram of an embodiment of the experience-based device and

Figure 2 is a flow diagram for the computer part of this' Device is.

The liquid mixture to be analyzed is introduced into the device from a source S ^, via line 10. This liquid mixture can come from one or more petroleum refining processes. The source S. can for example be a sample stream of the fresh feed to a catalytic reforming process to determine the octane rating of fuels and which usually consists of a mixture of naphthenes, aromatics and paraffins.

The liquid mixture to be examined exits line 10 via an electrically operated multi-way or switching valve 11. The switching valve 11 is via line 12 with a

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connected to a source S ₂ for a standard liquid mixture of known composition that is used to calibrate the device. In its first switching position, the valve 11 allows the liquid mixture to be analyzed to pass through, and in its second switching position it allows the calibration or comparison mixture to pass through. The outlet end of the switching valve 11 is connected via line 14 to the inlet of a metering valve 15, the outlet of which delivers measured samples of the liquid mixture to be examined. The metering valve 15 further includes a bypass line which is in communication with its inlet and which provides for an uninterrupted flow of the liquid mixture. The Uinwegleitung is connected via line 16 to a second metering valve 17, which also has an outlet for measured samples and a bypass line which is provided with a vent line 18 for the discharge of the liquid mixture from the device. As a result of this arrangement, either the liquid mixture to be examined or the calibration or comparison liquid is present in the bodies of the metering valves 15 and 17 at all times, while the other liquid leaves the device via the vent line 18. . '

The metering valves 15 and 17 are: conventional valves that Measure constant parts of the volume of the liquid and send predetermined individual sample quantities of the liquid mixture to their outlets hand over. The device can contain metering valves for sample quantities of 1-50 microliters. For the analysis of However, naphthenes are preferred metering valves that dispense approximately 10 microliters of liquid.

The outlet of the metering valve 15 is via line 19 with a Connected to vaporizer 20, where the samples are vaporized in the presence of a suitable carrier gas, such as hydrogen, that into the evaporator 20 from a source S, via line is initiated. In general, different Use carrier gases provided that their combination

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sotzung d.the chemical reaction to which the liquid mixture is subjected is not significantly impaired. However, for the analysis of the fresh feed from catalytic reforms, the use of hydrogen is preferred to prevent coking of the reforming catalyst used in the microreactor discussed later. The vaporized mixture goes from the vaporizer 20 via line 22 into a microreactor 23. The microreactor 2J contains a tube part which is filled with a suitable catalyst which triggers a chemical reaction in the liquid samples which converts a large part of the constituent of interest into a constituent , which can be distinguished or separated from the rest of the liquid mixture. For the analysis of naphthenes in liquids, which contain at least naphthenes and aromatics or naphthenes and pair affins, the microreactor 23 should preferably contain a steel tube about 1.52 m long and about 4.76 mm in diameter, which is covered with a platinum Reforming catalyst is filled in a grain size of about 35 to 80 mesh. The microreactor 23 is fastened in a temperature-controlled envelope, for example the furnace 24, which keeps the microreactor at a higher temperature. The choice of the temperature and the operating pressure in the device depends on the composition of the liquid mixture to be examined and is generally not critical. These operating conditions must of course be set so that the desired chemical reaction takes place. For the analysis of naphthenes, the preferred temperature of the microreactor 23 moves approximately in the range from 200 to 400 ° C., while the pressure amounts to approximately 3 »^ 5 atmospheres. Under these conditions, most of the naphthenes in the samples are converted into aromatics, which can be separated from the paraffin and other components. Therefore, the increase in aromatic content shows the naphthene content of the samples.

After you have implemented the samples in this way and

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Liquid component of interest can be determined or removed. has made separable, their concentration in the samples can be determined in various ways, for example by adsorption spectroscopy or gas chromatography. For the analysis of Haphthenen detection in a gas chromatography column preferred, which contains a suitable polar substrate.

A chromatography column 25 and an electrically operated conventional backwash valve 26 serve this purpose. The effluent of the microreactor 23 passes via line 27 into the first inlet 26a of the backwash valve 26, which contains another five openings, 26b-26f and the flow through the Forward and backward chromatography column 25 allowed. The fifth opening 26e of the backwash valve is via a line 29 connected to an evaporator 28. The evaporator 28 is in turn via line 30 to the inlet end of the chromatography column 25 connected. The third opening 26c is connected to the outlet of the chromatography column via line 31, the fourth 26d is connected to an outlet line 32 in connection and the second and sixth openings 26b and 26f are connected to one another on the outside by a pipe loop 33 »

In its first switching position, the first opening on the backwash valve 26 is connected to the second opening and his third opening is in connection with the fourth and finally there is a connection between the fifth and the sixth opening. When the valve 26 is in this switching position, the liquid mixture enters, including the carrier gas from the microreactor through the first opening into the Eückgiilyentil one, leaves it through his- Second opening, he enters ^ put 'through / the sixth opening an un> leaves the valve over, the fifth Opening, goes through line 29, the Vqrdkiipfer 28 and finally by the ^ chromatography - Säu3.e 25 in the forward direction. The liquid from the chromatography column is coming through line 31 ütyer the third opening in the .Ebackwash valve 'and exits through its fourth opening, namely into the exit

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discharge line 32.

When the backwash valve 26 is in its second switching position, the first opening is connected to the sixth opening.

s tones
bound, the second opening / with the third and the fourth opening with the fifth opening in connection. In this switching position of the valve, the chromatography column is backwashed by the carrier gas in line 27, which enters the backwash valve through the first opening and leaves it through the sixth opening, enters the valve again through the second opening and escapes through the third opening then via line 31> the chromatography column 25 and the evaporator 28 flows in the opposite direction, reaches the backwash valve through the fifth opening and finally leaves it through the fourth opening and the outlet line 32. The outlet line 32 is connected to a pressure regulator 34. For the analysis of naphthenes, a pressure in the range of 2.11 4.22 atmospheres is preferred. The pressure regulator 34 is connected to a suitable detector, for example a thermal conductivity detector 35, which checks the outflow from the chromatography column. The electrical signals from the detector 35 are slipped to a computer 38 which will be discussed in greater detail in connection with FIG. To determine the naphthene content in hydrocarbon mixtures, the chromatography column 25 should preferably contain a steel tube about 3 m long and about 6.35 mm in diameter, which is coated with ß, ß'-thiodipropionitrile on a carrier such as Chromosorb P with a grain size of 60 - 80 mesh is filled. In this configuration, the column holds the aromatic components of the samples, but allows the saturated and other components to pass through first. When the column is then backwashed, the trapped aromatics are determined as they go from the column in the reverse direction to the detector 35, the area under the curve for the measured thermal conductivity during the backwash being proportional to the aromatics content of the respective samples.

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The analysis of the above-mentioned mixtures includes the conversion of the naphthenes into aromatics. If the starting mixture contains significant proportions of aromatics, it is necessary to have this measured by the chromatography column before the reaction. In order to analyze such mixtures in which one constituent is converted by the microreactor into another constituent, a possibility must be created in the device for the direct analytical determination of the mixture before the reaction. For this purpose, the metering valve 17 tears off samples of the starting mixture and passes them via the evaporator, which is connected to the metering valve 17 by line 36, and from there via line 30 into the inlet of the chromatography column 25. The carrier gas runs through the evaporator 28 via line 29, which is connected to the backwash valve 26, which receives the carrier gas from the source S, via the evaporator 28 and the microreactor 24. The hydrogen source S ₇ . is connected to the detector 35 and line 39 in order to provide a comparison value for the thermal conductivity value of the chromatography column effluent, which is measured by the detector 35.

The calibration curve or the predetermined relationship between the thermal conductivity measured by the detector 35 and the concentration of the constituent of interest in the mixture can be determined analytically. This determination is quite difficult, however, since the constituent of interest cannot always be completely converted by the microreactor. It is therefore more expedient to use a standard calibration mixture of precisely known composition, in which the concentration of the component of interest is approximately as high as "in the mixture to be analyzed. This calibration mixture is supplied from a source Sp via line 12, the switching valve 11 and - when this is in its second switching position - passed to metering valve 15 and from there on.

The device is initially run through two passes of the Standard mixture calibrated. In the first test run it works

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Standard mixture through the microreactor and into the chromatography column for analysis. In the second run, the mixture is sent directly to the chromatography column for analysis. Once the calibration has been carried out, later or periodic calibrations can be carried out simply by sending the standard or calibration mixture through the microreactor, since all subsequent changes in the operating behavior of the device occur mainly in the microreactor as a result of the aging of the catalyst.

The device further contains a time control device 37, which contains the usual time program elements and the actuation of the various valves in a suitable sequence. This timing is usually not critical provided that that the residence time of the samples in the microreactor and the chromatography column is long enough.

For the analysis of napthenes in the fresh charge of kat a Iy ti see reformers, the following will be done for the time controller 37 Programs, preferred: The injection of a first sample of the mixture to be examined into the microreactor, the Sample flows through the Clx / Omatography column and in it for so long lingers so that the aromatics are adsorbed and the saturated components of the sample are eluted in the forward direction and then reversed the direction of flow through the chromatography column and backwashed the aromatic content of the sample and measured wix'd. A second sample of the mixture is then injected directly into the chromatography column and the sequence just described for determining the aromatics is repeated. The preferred time program for the above The analysis of naphthenes described is as follows: 1) In normal operation, i. i.e., out of calibration, remains the switching valve 11 in its first switching position,

2) the metering valve 15 is actuated for about 30 to 120 seconds, while a first sample of the mixture is in the microreactor one is injected,

3) while the sample is being converted and via the backwash

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valve enters the chromatography column, the backwash valve is activated in its first switch position for about 5-15 minutes held and then switched to the second position, in which it enables backwashing of the column,

4 ·) then the backwash valve remains in its second switch position for about seven to twenty minutes the aromatics pass through and are all detected by the detector,

5) the backwash valve is then switched to its first position,

6) then the metering valve 17 will last about 30-120 seconds actuated to make it a single sample of the liquid mixture which enters the chromatography column past the microreactor,

7) the back-flushing acil 26 remains for about 5-15 minutes

in its first switch position, in which there is the flow through the chromatography column in the forward direction and the elution of saturated constituents allows

8) then we '"*, the backwash valve 26 in its second switching position Bounded and allows reflux through the chromatography column and the determination of the aromatics,

9) the backwash valve 26 is then back to its first Switch position brought, and the cycle beginning with 2) above is repeated.

The switch valve is used for initial calibration of the device 11 in its second switch position and the previously described working cycle beginning with step 2) is carried out with the calibration or standard mixture. Periodic recalibrations can be carried out depending on the load on the device Carry out once a day or in advance. With this recalibration v / earth steps 2) to 5) carried out, and the switching valve 11 held in its second switching position. After completion of the calibration, the switching valve 11 is returned to its first switch position and the normal Work sequence followed again.

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The output signals from detector 35 are sent to computer 38 transmitted, inf.! em the predetermined calibration relationship between the generated signals and the concentration of the component of interest in the examined liquid mixture programmed. The computer 38 also speaks to the Cycle controller 37, so that it each of the detector 35 generated thermal conductivity signals in the correct Can interpret order. The following equation was found to have the aforementioned predetermined relationship which is based on the results of the calibration test:

m the

Xp =% proportion of the second component ia examined Mixture after the reaction,

x ^ =% content of the second component in the examined Mixture before reaction,

■ Zp =% content of the second component in the calibration mixture according to ' the reaction,

Zy, =% content of the second component in the calibration mixture before the reaction,

Yy, = % of the liquid constituent of interest in the calibration mixture, independently determined, such as by. Mass spectrometry,

Y =% of the constituent of interest in the examined mixture is.

It will be understood that the time cycle given above is only a suggestion for the analysis of naphthenes and can be appropriately changed as the length of the microreactor and the chromatography column changes. Similar changes can be made for the analysis of similar liquid odors. If one extends κ. B. the microreactor or the Chromatcgrafie column, this leads to increased residence time of the mixture and makes a change in the

209844/0486 BAD

Timing sequence necessary. You can also see the various automatic valves for which electrical actuation has been described, including pneumatically operated valves replace * In this case the time switch controller is replaced with the usual elek ^ rischZpnetiHaiiisciaen. Veirbilschaltera connected. Furthermore, various lines shown in FIG. 1 can be used are, by combining different devices. parts are left out. For example, you can use the Sample dosing valves and vaporizer in a single injector sum up. Furthermore, since the device is calibrated in the manner described above, the reaction needs im Microreactor not being complete, d. i.e., the response does not need to record the entire amount of the converted constituent in the liquid mixture. Then came the reaction detect more than one component of the liquid mixture, For example, in a mixture containing naphthenes, paraffins and aromatics, some of the paraffins can be reformed while some of the naphthenes are converted into aromatics. The device is then in the after calibration Able to determine the naphthene content of the mixture. In addition, the device can be used to use a different than determine the converted constituent of the mixture. Analyzed one z. B. a mixture of naphthenes and paraffins, In order to measure the paraffin content, the device can be calibrated in such a way that it detects the reaction of the naphthenes, the Paraffin content is determined indirectly. Furthermore, it goes without saying for those skilled in the art that one can use the device to produce a large number of mixtures can analyze by using the one used in the microreactor Catalyst and the packing material of the chromatography column modified accordingly. So you can z. B. as a catalyst a Edelrieta3-1 and as a column filler a silicone rubber use and thus the mercaptans in hydrocarbon mixtures determine as hydrogen sulfide. Another An example is the detection of olefins and / or aromatics in coal / water mixtures by hydrogenating them Olefins and / or aromatics.

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_0R , G! N *.

In FIG. 2, a computer is shown which can be used as the computer indicated in FIG. 1, the signals from detector 35 going to an integrator 50, which also receives signals from the time switch controller 37 and is therefore in de. Is able to distinguish the electrical pulses received by the detector during the duty cycle by time shifting. The integrator 50 integrates the area under each yar conductivity deflection and generates four corresponding output signals, namely Xpi ^x «i *> Zp and z ^., Which have already been explained in connection with equation (1). The signals Xp and x ^, are transmitted to a subtracter 51, the x. subtracts from Xp and generates an output signal corresponding to this difference, Xp - χ, -. This signal then goes on to a multiplier 5, the signals Zp and z- go from the integrator to a sub-tractor 55, which subtracts z * from Zp and generates a Zp - z corresponding output signal. The latter then goes to a divisor 5 ¹ ^ - U ^ to receive a signal which corresponds to the % -Qe content of the constituent of interest in the calibration mixture, a standard voltage source 55 is provided, which supplies a potentiometer 56 with constant voltage, which Hanc the position corresponding to the value X. The Y * signal generated in this way then goes to the multiplier 52, which multiplies the Y. signal with the difference signal from the subtractor 51 and a product of this Y- (x _o - x ^ This goes on to the divisor 54- which divides the signal by the difference signal from the subtractor 53 and generates an output signal corresponding to this quotient 5 ^ the concentration of the constituent of interest in the examined liquid mixture. This signal can be passed to a display or recorder and used to control the process by inputting it to an appropriate process control system.

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It is understood that the "described electrical Can replace computer elements with pneumatic elements. You can of course also use a digital computer An.Place the analog computer of Figure 2 for calculation use. L: in this case you can use the timer instead of the timer 57 preprogram the computer to controls all valve switching processes including the calibration cycles and the integration steps with the work sequence synchronized.

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Claims (1)

T 71 013 (D / 7P.511) Claims 1) J method for the analysis of liquid mixtures, in particular Hydrocarbons containing at least two components, the first component of which difficult because of its physical properties and the second component because of itself its physical properties can be more easily distinguished from the liquid mixture, since d u r c h marked that one a) the concentration of the second component in a sample of the liquid mixture is determined, b) subjecting a sample of the liquid mixture to a chemical reaction by which the first component of the mixture is at least partially converted into the second component, c) after this reaction, the concentration of the second component in the sample of the liquid mixture determined and d) from the concentrations measured according to a) and c) on the basis of a predetermined relationship between the measured contents of the second constituent and the concentration of the same constituents in one Comparison sample of a comparison mixture, a first signal for the concentration of the first component generated in the liquid mixture. 209 8 44/0466 2) The method according to claim 1, d a by ch characterized in that eir; second signal door the measured value according to a) and a third signal for the measured value according to c) is generated. 3) Method according to claim 2, d a d u r c, h characterized in that the predetermined relationship is characterized it is determined that one ' e) the concentration of the second component in one Measures the sample of the comparison mixture and generates a fourth signal for f) The sample of the comparison mixture also shows the chemical reaction among essentially the same Conditions of claim 1 b) subject and thereby the first component at least partially in the converts the second component, g) following this reaction, the concentration of the second component in the comparative sample of the 3? Liquid mixture is determined and a fifth signal is generated for it, and h) the second, third, fourth and fifth signals composed into a proportional relationship that the concentration of the second component in the comparison sample before and after reaction stage f) with the concentration of the second component in the liquid mixture before and after the resection stage according to claim 1 b) and. with the predetermined concentration of the first component in the sample of the comparative mixture connects. 4) Method according to claim Ι ·, characterized in that the union h) of the second, 209844/0486 third, fourth and fifth signals using the following equation: J, (xp - x.) occurs in the .Χ = the concentration of the first component in the Liquid mixture, y, = the concentration of the first constituent in the sample of the comparison mixture, ζ, - = the concentration of the second component in the Comparison mixture before the reaction, z _o = the concentration of the second component in the comparison mixture after the reaction, x- = the concentration of the second component in the Liquid mixture before the reaction and Xp = the concentration of the second component in the Mean liquid mixture after the reaction. 5) Method according to claim 1, characterized that the liquid mixture during the reaction according to b) at least partially to a temperature is heated, which thermodynamically favors reaction b). 6) The method according to claim 1, d a d u r c h characterized that the proportion of the second constituent in the fluid is determined by selective adsorption is, the reaction b) in the presence of a catalysis 2098U / Q466 ■. ■. - ri - tors is carried out and the determinations a) and c) are carried out by chromatography. 7) Method according to one of claims 1-6, characterized in that naphthenes are contained in the liquid mixture as the first component, the reaction, b) in the presence of a noble metal catalyst and. V / a sserstof fs carried out while at least a portion of the naphthenes is delt umgewai in aromatics and at least in part, the Probe.des b during this reaction) liquid mixture to a temperature of about 200-400 ⁰ C is heated. 8) Method according to one of claims 1 - 7> d a d u r c h that a liquid mixture is analyzed, which consists essentially of aromatics, naphthenes and paraffins. 9.) The method according to any one of claims 1-8, characterized in that the first component The liquid mixture contains the naphthenes and, as a second component, the aromatics and each of the Method steps a), c) and g) an examination of the respective sample by introducing the samples into a Gas chromatography column with the aid of a carrier gas, adsorption of the aromatics on the column filling, expulsion the remaining components from the column in flow ft r Richtungf'cles- inert gas and measurement of at least one physical property of the column drain at the front End, for determining the aroma concentration in the sample of the liquid noise includes. 10) device for performing the method: according to claim 1, - 9 »'g e-k, e'fi.n ζ e i 6 h η e t through: * Driving out the aromatics by reversing the direction of flow. 209844/0486 a) one through which the liquid mixture flows, with a . '' Catalyst-filled reactor chamber (23) for converting the first component of the liquid mixture into the second component, b) one connected to the inlet end of the reactor chamber (23) Source. (S-O for the carrier gas that transports the liquid mixture through the chamber (2J), ' c) a heating device (24) connected to the chamber (23), d) a gas chromatography column (25) and a detector (35) ι both connected to the outlet end of the chamber 23 and set up to determine the concentration of the first component in the liquid mixture by measuring the converted proportion of this first Be component, e) a source (S ^) for the comparison mixture with known Concentration of the first component, and fValve devices (11, 15)? which are connected to the source (Sp) for the reference or calibration liquid and the reactor chamber (23) and the . equal liquid for the purpose of calibrating the device periodically Introduce into the reactor chamber. 11) Device according to claim 10, characterized that the valve device (11) with the source (S ^ ₁ ) for the subject to be investigated 'en is mixed and has two switch positions / where in the first switch position da-s to be examined Mixture for the purpose of determining its first component and the comparison mixture in the second Schaltatollung for the purpose of calibrating the Ger / i fco, and das.Ventil BADOBlGlNAiL. (11) is also connected to a metering valve (15), - the periodic samples of the baw to be examined. of the comparison mixture with an approximately constant volume and injected into the reactor chamber (23), so, ^T ie an evaporator (20), which is arranged between the metering valve (15) and reactor chamber (23) and with the source (S ₇ ) for the carrier gas connected is. 12) Device according to claim 11, further g e k e η η ζ e i cli » net through facilities (11, 15, 17, 28) that work with the source (S ^) for the mixture to be examined and connected to the gas chromatograph (25) and the latter evaporated samples of the unreacted test mixture for the purpose of determining the second constituent. 15) Device according to claim 12, far-ex- gekenna ei chnet through a with the inlet and outlet ends of the Gas chromatograph (25) connected backwash valve (26), which is in communication with a detector (35) and the reactor chamber (23), 14) Apparatus according to claim 13, characterized in that the reactor chamber (23) is a steel tube about 1.52 m long and about 4,? 6 mra diameter, which is filled with a platinum reforming catalyst in the grain size of about 35-80 mesh is, contains and is surrounded by a heating device (24), with which the temperature of the chamber (23) is kept at about 200 - 400 ^G C, and the ear chromatography column (25) a chair tube of about 3 ή length-e and about 6.35 mm in diameter, which is filled with β, β'-thioclipropionitrile on a support with about 60-60 mesh grain size for ^{adsorption of Ax 1 OKIaten, and, cip.r detector (35) f-ine device.} It also contains the generation of a signal, the time integral of which gives the concentration of the aromatics in the liquid samples, and that furthermore BATH ORIGINAL a pressure regulator (34) connected to the outlet of the column (25) is connected and the pressure in the column (25) and the collector chamber (23) "at about 2.11 - 4.22 atmospheres holds, and. a computer (38) is provided which has an integrator (50) contains v / which is connected to the detector (35) and the concentration of the first Constituent in the overall mixture based on the predetermined calibration relationship: (ζ - ζ) £ - 1 determined (in which the symbols have the meaning given above), 15) Device according to claim 14, d a d u r c h g e k e η η- " draws. that the computer system (3B) the following Elements includes: a device (56) for manual input of the predetermined \ vrrts (Y ^) the plonentration of the first component in the comparison mixture and to generate a second signal for this concentration, an integrator ( ^r 0) for integrating the signals of the detector (55) and for generating a third, fourth and fifth signal for the concentration of the detected second constituent in the test mixture, these signals z, ,, 3 ^, X _n and x _p correspond, a first Sut-traktpr (53) »^ ^he ÖIE of" integrator (50) komrienöen fourth and fifth signals for 2 and z ~ in a seventh signal for the difference (zp - ζ ^ BATH ORIGINAL a second subtractor (51)? the one from the integrator (50) incoming fifth and sixth signals for Xp and X _x , converted into an eighth signal for the difference (xp - x.), a multiplier (52) associated with the second subtractor (51) and the manual input device (56) and au.s their signals a ninth signal for the product Y _x . (x ~ - ^ O generated, a divisor (5 ^) ₅ which is connected to the multiplier (52) and the first subtractor (55) and generates a first output signal from the ninth product signal and the seventh difference signal, which according to the calibration relationship of the concentration of corresponds to the most constituent part in the mixture under investigation. 209844/0486 55 " Blank page