DE102006053078A1 - Apparatus and method for the continuous transfer and analysis of fluids - Google Patents

Abstract

The present invention relates to an apparatus and method for the continuous transfer of product fluids from reaction spaces. The device contains an arrangement of at least two high-pressure separators, which are in operative connection with a respective low-pressure separator / low-pressure region. The respective connection from the high pressure to the low pressure area is equipped with a restrictor. In preferred embodiments of the device, the side of the low-pressure region is equipped with a rectification column, the gas line emerging from the rectification column being combined with the gas line of the respectively associated high-pressure side via a gas mixer to form a line. In a preferred embodiment, the process according to the invention is carried out under conditions under which cyclic and / or oscillating pressure fluctuations occur in the high-pressure region of the apparatus. The oscillating pressure fluctuations are preferably used for process control and / or for controlling the method.

Description

The The present invention relates to an apparatus and a method for testing the reactivity of solid catalysts, which are preferred for characterization of multicomponent mixtures and to optimize reaction conditions be used. In the present case, preference is given to multicomponent mixtures, analyzed or processed, the at least two not completely miscible contain fluid phases. The multicomponent mixture is preferred a product fluid from a reaction space.

at a variety of chemical processes fall multicomponent mixtures For example, from process systems in analysis systems to are transfer. Multicomponent mixtures typically have separation steps or be subjected to a product work-up. Multi-component mixtures are preferred separated in separators, for example, the liquid and the gas phase are separated from each other.

Prefers become the device according to the invention and the method according to the invention in connection with the investigation of petrochemical processes used. These processes preferably include desulfurization ("Hydrodesulfurization") and denitrogenation ("Hydrodenitrogenation") preferably of oils, vacuum gas oils or Diesel and hydroprocessing ("hydroprocessing, hydrotreating, Hydrocracking ") again preferably oils and vacuum gas oils. Furthermore it is preferred that the device according to the invention and the method according to the invention for the investigation of gas-to-liquid conversions (e.g., Fischer-Tropsch processes) is used.

An overview of the technical field to which the present application relates, for example, in the WO 2005/063372 and in the DE 103 61 003 B3 given. These rights relate to apparatus for the parallelized testing of catalysts under high pressure, which produce multicomponent mixtures with components of different volatility. Upon exiting the high pressure multicomponent mixtures (product fluids) from the reaction spaces, they are first collected in high pressure separators, with the particularly volatile components of the fluid being diverted via gas exit lines of the high pressure separator and fed to an analysis unit. According to one embodiment, each individual high-pressure separator in each case has a gas outlet line for more volatile components. After a certain amount of less volatile product fluid has separated in individual high-pressure separators, this is periodically emptied by opening a valve which is located within the discharge line, which is attached to the bottom of the high-pressure separator. However, it is to be regarded as a disadvantage that no continuous operation is possible by the periodic opening and closing of the valve or the valves. Such operation is advantageous for certain chemical reactions. Furthermore, valves - especially at high reaction temperatures - susceptible components whose use is preferably avoided or minimized.

A the tasks of the invention it is therefore necessary to provide a device and a method with which product fluids in volatile and less volatile Components separated and possible in a continuous manner different recording areas or Supplied to analysis units can be.

A Another object is the susceptibility of the apparatus in terms of to improve the mechanical strength of individual components. About that In addition, the inventive method be designed in such a way that the method by means of a suitable process control semiautomatic as possible or fully automatic leaves.

• (a) zumindest zwei parallele Reaktionsräume (20');
• (b) pro Reaktionsraum (20') zumindest eine reaktionsraumausgangsseitige Verbindung (81) zu zumindest einem Hochdruck-Abscheider (80);
• (c) pro Reaktionsraum (20') zumindest einen Hochdruck-Abscheider (80);
• (d) pro Hochdruck-Abscheider (80) zumindest eine Verbindung (84) zu zumindest einem Niederdruckbereich oder zu zumindest einem Niederdruck-Abscheider;
• (e) pro Hochdruck-Abscheider (80) zumindest eine Ausgangsverbindung (82) für im Wesentlichen gasförmige Verbindungen, die zu einer Analyseneinheit (40) führt;
• aktionsraumausgangsseitigen Hoch(f) im redruckbereich, d.h. entweder zwischen Ausgang des Reaktionsraumes (20') und Hochdruck-Abscheider (80) oder am Hochdruck-Abscheider, jeweils pro Einheit „Reaktionsraum-Hochdruck-Abscheider", eine Verbindung zu einem (Druck-)Haltegas (50) sowie optional eine Verbindung zu einem (Druck-)Regelfluid (60).

The objects mentioned here and further are achieved by providing a device for transferring and / or analyzing multicomponent mixtures, which comprises at least the following components:

• (a) at least two parallel reaction spaces ( 20 ' );
• (b) per reaction space ( 20 ' ) at least one reaction space exit-side compound ( 81 ) to at least one high-pressure separator ( 80 );
• (c) per reaction space ( 20 ' ) at least one high-pressure separator ( 80 );
• (d) per high-pressure separator ( 80 ) at least one compound ( 84 ) to at least one low-pressure region or to at least one low-pressure separator;
• (e) per high-pressure separator ( 80 ) at least one starting compound ( 82 ) for substantially gaseous compounds which form an analytical unit ( 40 ) leads;
• action space exit side high (f) in the redruck range, ie either between the exit of the reaction space ( 20 ' ) and high-pressure separator ( 80 ) or at the high-pressure separator, in each case per unit "reaction space high-pressure separator", a connection to a (pressure) holding gas ( 50 ) and optionally a connection to a (pressure) control fluid ( 60 ).

It is preferred that each compound ( 84 ) at least one low-pressure region or low-pressure separator each have at least one restrictor ( 83 ) and more preferably contains no valve.

The restrictor ( 83 ) preferably allows the continuous removal of product fluid and allows the abandonment of otherwise necessary components such as valve and / or low-pressure separator. Thus, the device according to the invention not only allows a simpler, but also a less susceptible to interference operation and in particular a continuous operation.

• (g) an zumindest einer Verbindung (84) stromabwärts hinter dem Restriktor (83) auf der Niederdruckseite zumindest eine Rektifikationskolonne (80'), die vorzugsweise mit Gaszuleitung (96) und Ableitung (97) ausgestattet ist;
• (h) zumindest eine Verbindung (83') von der Rektifikationskolonne (80') zu zumindest einen Aufnahmebereich und/oder Analysenbereich für wenig(er) flüchtige Fluide;
• (i) pro Reaktionsraum (20') eine von der niederdruckseitigen Rektifikationskolonne (80') abgehende Gasleitung (97), welche mit jeweils einer zugehörigen hochdruckseitigen Gasausgangsleitung (27) und jeweils einem Gasmischer (95) in Wirkverbindung steht, wobei die Ausgangsleitung des Gasmischers (95) vorzugsweise zu einer Analyseneinheit (40) führt.

In a further preferred embodiment, the device according to the invention has at least one further of the following components:

• (g) on at least one compound ( 84 ) downstream of the restrictor ( 83 ) on the low pressure side at least one rectification column ( 80 ' ), preferably with gas supply ( 96 ) and derivation ( 97 ) Is provided;
• (h) at least one compound ( 83 ' ) from the rectification column ( 80 ' ) to at least one receiving area and / or analysis area for little volatile fluid (s);
• (i) per reaction space ( 20 ' ) one of the low-pressure side rectification column ( 80 ' ) outgoing gas line ( 97 ), each with an associated high-pressure side gas outlet line ( 27 ) and in each case a gas mixer ( 95 ) is in operative connection, wherein the output line of the gas mixer ( 95 ) preferably to an analysis unit ( 40 ) leads.

With Help of the preferred components (h) or (h) and (i) it is in a preferred embodiment of the method according to the invention possible, Product fluid in countercurrent with an inert gas / stripping gas continuously to work on. This preferred embodiment is in particular for applications in the "Hydroprocessing" area suitable.

In a preferred embodiment, there is between the individual compounds, which are different from the different gas mixers ( 95 ) to the analysis unit ( 40 ), a multiport valve ( 30 ). The gas supply line ( 96 ) is preferably the supply of inert gas / stripping gas, the gas discharge ( 97 ) preferably for the derivation of the same.

Is the device according to the invention without rectification column ( 80 ' ), it is located between the respective output connections ( 82 . 27 ) and the analysis unit ( 40 ) preferably a multiport valve ( 30 ).

In a preferred embodiment, the common holding gas supply ( 50 ) in such a way that it comprises, per reaction unit, in each case one reaction space and the holding gas supply attached on the reaction chamber outlet side, each with one pressure measuring device per connection ( 82 ) ( 200 . 300 , ...) is in operative connection.

• (i) Abscheiden von zumindest einer Multikomponenten-Mischung, die aus zumindest zwei parallelen Reaktionsräumen (20') austritt, in jeweils einen diesen zugeordneten Hochdruck-Abscheider (80), welcher in Wirkverbindung (84) mit einem Niederdruckbereich und/oder einem Niederdruckabscheider steht;
• (ii) Überführen von leicht(er) flüchtigen, im Wesentlichen gasförmigen Komponenten eines Produktfluids über eine Ausgangsverbindung (82) für gasförmige Verbindungen des jeweiligen Hochdruckbereichs des Hochdruck-Abscheiders (80) zu einer Analyseneinheit (40);
• (iii) Überführen von wenig(er) flüchtigen Komponenten eines Produktfluids aus dem Hochdruck-Abscheider (80) über eine am Hochdruck-Abscheider befindliche bodenseitige, mit Restriktor (83) versehene Ausgangsleitung zu einem Niederdruckbereich (84).

The above objects are also achieved by a method for continuously transferring product fluids from the high pressure region of at least two parallel reaction spaces comprising at least the following steps:

• (i) separating at least one multicomponent mixture consisting of at least two parallel reaction spaces ( 20 ' ), in each case one associated with this high-pressure separator ( 80 ) which is in active connection ( 84 ) is at a low pressure area and / or a low pressure separator;
• (ii) transferring slightly volatile, substantially gaseous components of a product fluid via a starting compound ( 82 ) for gaseous compounds of the respective high-pressure region of the high-pressure separator ( 80 ) to an analysis unit ( 40 );
• (iii) transferring little (s) volatile components of a product fluid from the high pressure separator ( 80 ) via a high-pressure separator located on the bottom side, with restrictor ( 83 ) provided output line to a low pressure area ( 84 ).

It is preferred that step (iii) is carried out continuously and / or so that during the transfer of product fluid a state is established in which a pressure sensor for the holding gas supply ( 50 ) a cyclic and / or oscillatory pressure change is measurable. Further, it is preferred that step (iii) be accomplished without the use of a valve in the exit line (FIG. 84 ) is carried out. If a particularly high proportion of gaseous fluid should be present in the product fluid, it may be possible to use a valve for additional control.

• (iv) Überleiten des aus der Ableitung (84) des Hochdruck-Abscheiders stammenden Produktfluids über eine Rektifikationskolonne (80'), die vorzugsweise mit einem Stripgas durchspült wird;
• (v) Zuführen des aus der Rektifikationskolonne (80') austretenden Stripgases zu einem Gasmischer (95) unter Vereinigung des Stripgases mit dem leichter flüchtigen Produktfluid, welches aus der Ausgangsverbindung des Hochdruckbereichs (82, 27) entstammt;
• (vi) Zuführen der im Gasmischer (95) vereinigten Gase zu einer Analyseneinheit (40) für gasförmige Komponenten.

In a preferred embodiment, the method comprises at least one further of the following steps:

• (iv) passing the from the derivative ( 84 ) of the high-pressure separator product fluid via a rectification column ( 80 ' ), which is preferably flushed with a stripping gas;
• (v) feeding the product from the rectification column ( 80 ' ) exiting stripping gas to a gas mixer ( 95 ) combining the stripping gas with the more volatile product fluid, which from the starting compound of the high pressure region ( 82 . 27 ) comes from;
• (vi) feeding the in the gas mixer ( 95 ) combined gases to an analysis unit ( 40 ) for gaseous components.

A mode of operation, which is preferably selected for carrying out the method according to the invention, relates in each case to the change between entry of substantially gaseous fluid and entry of substantially liquid product fluid into the zone with restrictor element ( 83 ) provided on the bottom side mounted derivative ( 84 ) of the separator ( 80 ). As a result, preferably occur low (cyclic) pressure fluctuations within the high pressure range of the apparatus. The term "low" in this context means that the size of the pressure fluctuations is less than 1% of the process pressure on the high-pressure side (which essentially corresponds to the internal pressure of the reactors), wherein pressure fluctuations of less than 0.5% and also less than 0, 02% are more preferred ..

The total pressure in the high-pressure region of the apparatus can assume values between 5 and 500 bar, with pressure values between 45 and 180 bar being preferred. The pressure fluctuations are preferably registered via a pressure sensor or via a pressure monitor which, in conjunction with the holding gas fluid supply ( 50 ) stands.

The inventive method is thus preferably carried out in a manner in which the (low) Pressure fluctuations between the pressure rise and the pressure decrease, which by the way of the continuous fluid outlet caused by the restrictor element in the discharge of the separator are changing in a cyclic way ("oscillating").

The Duration for a cycle for minor Pressure changes, consisting of pressure rise and pressure drop, is preferably in a range of 0.1 to 150 seconds per cycle, with one range from 2 to 80 seconds per cycle is more preferred. One cycle is running from maximum pressure to maximum pressure (end of pressure increase) resp. from minimum pressure to minimum pressure (end of pressure drop). These Oscillating operation is in the operation of the device with Valves on the product fluid output line of the high-pressure separator not found and so can not be expected. The surprising oscillating effect probably results from the invention-specific combination device features (d) and (f), wherein the present invention is not limited to this proposed mechanism.

3 shows a preferred embodiment according to which the oscillations are measured individually for each. The measurement of oscillations in the reaction spaces can be done in two different ways. Either by the measurement of the flow or mass flow of the pressure hold gas or by the measurement of the pressure in the pressure hold gas line at a constant volume flow of the pressure hold gas. A disadvantage of this variant, however, is that it can not be concluded by an individual volume flow or pressure measurement on an individual reactor, but only the average behavior of the reactors is detected. If an individual evaluation of a reactor is to take place, the pressures in the pressure-holding gas lines for the individual reactors must be recorded separately. Furthermore, a decoupling of the outgoing lines from the supply line is required. The decoupling is achieved by check valves or flaps ( 220 ).

According to the present Invention, an operation of the device is particularly preferred, at which pressure fluctuations in cyclic or oscillation-like Form occur. Based on the oscillatory signals can be recognize if the process is stable and / or desired Condition is running. About that can out the oscillatory signals are also used specifically for process control be as a change of Process parameters usually based on the change of the oscillatory Signals is recognizable.

In connection with the transfer of the fluid from the high-pressure separator in the low-pressure region, there is usually a relaxation of the fluid or gaseous compounds dissolved in the liquid fluid, in which at least a portion of these volatile components in the gas phase (can). In order to remove the highly volatile gaseous constituents as completely as possible from the liquid product fluid, the liquid product fluid is passed in a preferred embodiment via a rectification column. The rectification column ( 80 ' ) is preferably operated in countercurrent with inert gas / stripping gas. As a result, the (less volatile) gaseous components dissolved in the fluid are for the most part expelled from the liquid fluid. This embodiment is for example in 2 shown.

In a preferred embodiment of the present invention, the gaseous components present on the low pressure side ( 84 ) and by rectification column ( 80 ' ) are withdrawn from the product fluid, with an inert gas / stripping gas via a gas discharge ( 97 ) at the upper end of the rectification column to a gas mixer ( 95 ). In the gas mixer, the gas stream coming from the low pressure side is preferably mixed with the gaseous fluid coming directly from the outlet for gaseous compounds from the high pressure side ( 27 ), united and an analysis unit ( 40 ).

According to a preferred embodiment of the method according to the invention, the largest proportion of gaseous fluids which emerge from the high-pressure region of the apparatus leaves it via the starting compound for gaseous components (US Pat. 82 ). Preferably, the restrictors ( 25 ' ) for the starting compound ( 82 ) and the restrictors ( 83 ) at the bottom end of the high-pressure separator ( 80 ) designed so that through the starting compound ( 82 ) for gaseous compounds preferably each more than 80% of the total amount of gas leak, the total of the reaction is released, more preferably more than 90% of the total amount of gas.

Under a "restrictor" within the meaning of the present Invention is to understand each component, which flows through with a fluid opposite this represents a measurable flow resistance. "Measurable" means that the flow resistance of each restrictor, at least more than a factor of 2, is preferred by at least more than a factor of 5, more preferably by more than the factor 10 is larger as the flow resistance of any other component (component) in the device, except other restrictors.

Become Restriction reaction chamber input side used, so should in inventive method preferably a pressure drop of at least 2 bar are generated, continue preferably a pressure loss of at least 5 bar, more preferably of at least 10 bar. The pressure loss is the difference "pressure in front of the reaction space "minus the Pressure after the reaction space.

If the restrictors are used on the reaction chamber exit side, and if they are used in addition to fluid equalization also for "relaxing" the pressure prevailing in the reaction chambers to the pressure of the components which are optionally downstream of the reaction chambers, then a pressure loss of at least 10 bar should preferably be used in the process according to the invention be carried out, preferably of at least 20 bar.For the presently particularly preferred restrictors ( 83 ), the characterization preferably takes place via the LHSV (Liquid Hourly Space Velocity).

Smallities of restrictors are preferably grouped according to their functional identity as "sets" (or "groups"). A set is preferably a plurality of at least two restrictors, which may belong together spatially and / or functionally together, but which in any case have the same functionality within the device according to the invention. Thus, for example, all input or all output side to the reaction chambers or subsets of reaction chambers associated restrictors such a set. Accordingly, the device according to the invention preferably comprises a set of restrictors, each of the Eduktflüssigkeitszufuhr or the Regelfluidzufuhr or the holding gas supply or the derivatives ( 84 ) are assigned for gaseous components.

Restrictors within the meaning of the present invention are preferably metal plates with bores, sintered metal plates, pinholes, micromachined channels, capillaries and / or frits (porous materials, in particular sintered ceramic frits) ("passive restrictors"). ) Restrictors ( 15 ) in the reaction-chamber-inlet-side region should preferably be the flow of the inflowing fluid ( 10 ) and ensure an extensive uniform distribution of the inflowing fluids across the individual connections.

For the restrictors ( 83 ) in the derivative ( 84 ) capillaries are preferred. A capillary is preferably made of "fused silica" material, the inside diameter of the capillary is preferably in the range of 5 to 250 μm, more preferably 10 to 150 μm, the length of the capillary is preferably in the range of 0, 01 to 20 m, more preferably in a range of 0.1 to 10 m.

One Blocking the restrictor elements by solid particles (e.g. Katalystorfeinstaub) should preferably be avoided or minimized become. For this purpose, the catalyst material in the reaction space is preferably stored on fine-meshed nets and / or frits, through which only fluids and no solid particles can pass through.

The specific characteristics of the restrictors ( 83 ) are of importance for carrying out the method according to the invention. These depend, for example, on the pressure and temperature conditions at which the liquid product fluids are transferred from the high-pressure to the low-pressure region, as well as the viscous properties of the product fluids themselves.

Based on the characteristics of the respective restrictor elements ( 83 ) under selected experimental conditions, preferably a suitable educt fluid feed rate is determined, wherein the feed rate of educt fluid should generally be lower than the rate of product fluid outflow through the restrictor element ( 83 ) on the bottom side of the separator ( 80 ). The educt fluid supply is preferably carried out in such a manner that a defined inlet pressure is set, which is almost, or completely, constant under the respectively selected conditions. Suitable educt fluid delivery rates based on the supply of liquid educts and expressed by LHSV - are preferably in a range of 0.1 to 20 h ^-1 , more preferably 1 to 8 h ^-1 .

In the event that the product entry rates in the separator ( 80 ) are significantly smaller than the maximum possible discharge rates, usually occurs predominantly gaseous fluid from the with restrictor element ( 83 ) provided on the bottom side arranged derivative ( 84 ), this gaseous fluid essentially consisting of the holding gas supply ( 50 ) and / or the control fluid supply ( 60 ) comes from. When introducing larger amounts of product fluid into the separator ( 80 ), correspondingly lower amounts of gaseous fluid from the bottom side arranged derivative ( 84 ) out.

In a further preferred embodiment of the device according to the invention, the holding gas supply ( 50 ) to each individual reactor or high pressure area, each with one pressure measuring device per connecting line ( 200 . 300 , ...) fitted.

When using (passive) restrictors ( 83 ) between the high-pressure and low-pressure ranges, these can be used either in conjunction with a valve ( 87 ) or without valve in the drainage. In the event that a valve ( 87 ) upstream of the passive restrictor, it is possible that the transfer of product fluid during the process is changed by the closing of the valve from the continuous to the discontinuous state. A discontinuous operating state can, for example, then be desired if maintenance work is to be carried out on the apparatus without interrupting the processes taking place within the reactors.

It is further preferred that at least one derivative ( 84 ) of the bottom-side (low-pressure side) Abscheiderauslaufs each with at least one detector ( 201 . 202 , ...), by means of which the flow of product fluid can be monitored by the passive restrictor element. As detectors are preferably photocells, which can operate in the mode of reflection, refraction or absorption.

in the Can operate the capillaries increased temperatures exhibit. Because of these elevated temperatures It is advantageous for the capillaries to move the light barrier by means of light guides to couple to an optics / electronics unit, so that they are not the raised Temperatures is exposed, which prevail directly at the capillary. In addition to the use of optical sensors is also a use of acoustic or dielectric sensors as well as of vibration sensors prefers.

By means of the said detectors can - in addition to the possible small pressure fluctuations within the high pressure area of the system - determine whether at any given time t ₁ (essentially) of gaseous fluid, or (essentially) liquid product fluid through the pipe portion at the position of the derivative flows. The values measured in this case are recorded by means of a process control unit and are preferably used - in addition to recording the pressure fluctuations as described above - for control or for process monitoring.

there it is preferred that a detector element is selected, whose response time is shorter as the cycle duration of a respective pressure fluctuation.

The more volatile, essentially gaseous fluids which are present at the high-pressure separator ( 80 ) and via the starting compound ( 82 ) a unit for analysis ( 40 ) are also referred to as hot gas or permanent gas. Preferably, these light (or lighter) volatile gases contain at least one of the following components: hydrogen, methane, carbon monoxide; C ₂ components ethane, ethene, ethyne; Carrier gases; SO _x or NO _x . By suitable process management, in particular by restrictor elements ( 25 ' ) in the starting compound ( 82 ), the escape of gaseous components, which have a lower volatility, largely suppressed at this point, so that these components remain initially dissolved in the fluid. This means that the fluid present in the high-pressure separator preferably acts as a matrix in which gaseous components can be partially retained in accordance with their solubility or volatility under the respective process conditions.

In a further preferred embodiment of the process, the volatile gaseous components which are present via the compound ( 82 ) from the high pressure area ( 80 ), directly or via a multiport valve ( 36 ) a unit for analysis ( 40 ) to qualitatively and quantitatively determine the composition of the more volatile components. To determine the hydrogen content and other components contained in the product gas stream, for example, a gas chromatograph can be used, which is preferably equipped with a thermal conductivity detector. Other detection methods include carbon analyzer, IR, UV VIS, Raman.

By removing light (gaseous) volatile gaseous components already at the high-pressure separator ( 80 ) is a downstream analysis unit, which is connected to the low pressure area, relieved. Furthermore, volatile gases (eg H ₂ , H ₂ S, methane, ethane, ethene, etc.) preferably require other analysis methods (eg TCD, FID, thermal conductivity detectors) than higher volatile gases (ionization, eg FID).

Brief description of the figures:

1 shows a schematic representation of an apparatus with eight parallel reaction spaces ( 20 ' ), each of which is equipped with a high-pressure separator ( 80 ) and subsequent low-pressure area ( 84 ) connected is. In the high-pressure separator ( 80 ) arising gaseous components are over with restrictors ( 25 ' ) ( 82 ) derived. The gases thus transferred are released via the connections ( 27 ) and a multiport valve ( 30 ) to an analysis unit ( 40 ) or to an output line ( 45 ). In the low pressure area after the separator ( 80 ) are restrictors ( 83 ).

2 shows a schematic representation of an apparatus with eight parallel reaction spaces ( 20 ' ), each containing a combination of high-pressure separator ( 80 ) and low pressure region, wherein the respective connecting line ( 84 ) on the low pressure side a rectification column ( 80 ' ) is connected downstream.

3 1 shows a schematic representation of an apparatus with three reaction spaces, in which each individual high-pressure area is in each case provided with a separate pressure monitor (FIG. 200 . 300 . 400 ), each with the gas outlet line ( 27 ) connected is. To the rectification column ( 80 ' ) are supply lines ( 96 ) and derivatives ( 97 ) for strip or intergas. The derivative ( 97 ) connected to the high-pressure side gas outlet line ( 27 ) is connected via a gas mixer ( 95 ) to an analysis unit ( 40 ).

4 1 shows a schematic representation of an apparatus with three reaction spaces, in which each individual connecting line ( 84 ) with capillaries from the high pressure side to the low pressure side with an optical monitoring unit ( 201 . 301 . 401 ) Is provided.

5 shows a schematic representation of an apparatus with two reaction spaces, in which each connecting line ( 84 ) with an optical sensor ( 201 ), a PID controller ( 203 ), a valve for metering a cooling fluid ( 204 ) and a cooling line ( 205 ) for cooling the capillary ( 83 ) Is provided.

in the Following are essential technical terms, as used in the used in the present invention and not immediately to follow from the expertise explained become.

Under a "gas phase reaction" within the meaning of the present Invention is a chemical reaction to understand in which all starting materials and products under reaction conditions are present as gases.

Under a "liquid phase reaction" within the meaning of the present Invention is a chemical reaction to understand in which all starting materials and products are liquid under reaction conditions.

Under a "multi-phase reaction" within the meaning of the present Invention is a chemical reaction to be understood under reaction conditions in the presence of at least two different phases that are not Completely are miscible with each other, expires. The phases can all or part or all of them liquid and / or solid and / or be gaseous. The phases can Be educts or products or both. The with the help of the present Apparatus for reactions to be investigated may be gas-phase, liquid-phase or multiphase reactions.

Under the term "multicomponent mixture" is defined in the sense of present invention, any mixture of at least two components to understand which by physical or physico-chemical Process, or combinations thereof, at least partially from each other can be separated. Of these, in particular mixtures of at least two are not Completely miscible liquid Phases or mixtures of at least one gaseous phase and at least one liquid Phase as well as emulsions, dispersions or suspensions to understand.

For the purposes of the present invention, a "non-volume-constant reaction" is to be understood as meaning any chemical reaction in which the number of moles of gaseous substances per formula conversion changes and / or the volume is solid / solid, solid / liquid, liquid / liquid due to a conversion , liquid / gaseous or gaseous / gaseous (in non-ideal gases) increases or decreases. For non-volume constant reactions, a device with holding gas supply ( 50 ) is particularly preferred.

For the purposes of the present invention, the term "high pressure" is to be understood as meaning any pressure which is higher than the pressure which prevails on the downstream side of a component upstream of the high pressure separator, in a range of 5 to 500 bar, and preferably there is a pressure in the range of 20 to 250 bar and more preferred is a pressure in the range of 90 to 150 bar. With regard to the pressure range on the high-pressure side of the apparatus or reactor and high-pressure separator are set no firm limits, but by the choice of certain materials and constructive features may have a certain limit on the pressure upper limit, which the skilled person taking into account the materials recognizes.

Under The term "low pressure" is in the sense of to understand the present invention, a pressure that is lower as the pressure on the upstream (in Reference to the educt current) directed side of a component. Of the Pressure on the low pressure side of the device, i. preferably downstream of the high-pressure separator, is preferably at least 0.5 bar lower as the pressure on the high pressure side of the device. Prefers the pressure on the low pressure side is in a range of 0 to 20 bar, more preferably in a range of 0 to 10 bar.

One "easy (he) volatile gaseous Component "is preferably a gas which is already in the high-pressure separator in gaseous Condition exists or passes into these.

A "fluid" within the meaning of the present Invention is any substance in which the elementary (molecular) Ingredients that make up the substance, for example, elements or molecules, but also agglomerates thereof, move against each other, and in particular have no fixed long distance order to each other. among them fall in particular liquids or gases, but also waxes, oils, Dispersions, fats, suspensions or melts. Unless the medium in liquid form is present, multiphase liquid systems are understood as fluids.

Under The term "valve" is within the meaning of the present Invention to understand each component, which allows one Reduce fluid flow, including these to stop bring.

A "common educt feed" in the sense of the present invention means any type of feed in which at least one educt is supplied to at least two reaction spaces spatially connected to a feed, in such a way that the reaction spaces are simultaneously and jointly exposed to the at least one educt The common educt feed ( 12 ) is located in front of the reaction chambers ( 20 ' )

Under a "educt gas" within the meaning of the present Invention is to be understood as meaning any gas or gas mixture which the reaction spaces, or Subsets thereof, (via a common Eduktzufuhr) can be supplied. The educt gas can, does not have to contain an inert gas and / or an admixture, as an internal standard for determining certain properties (For example, gas flow, etc.) can serve. The educt gas preferably contains at least one component that is involved in the chemical Reaction participates. The educt may also contain liquid components.

Under a "product" or "product fluid" within the meaning of the present invention Invention is to be understood as meaning any fluid or fluid mixture as well each disperse phase (which may also be solid constituents may contain), which / at least one reaction space dissipated and can be analyzed. The product may or may not have, but educt contain. The product may or may not be a fluid reaction product the reaction, which took place in a reaction space, contain.

In a preferred embodiment is the product a gas or a gas mixture, or a liquid, which contains a gas dissolved physically or chemically. Is the product a gas or a gas mixture, it is called a "reaction gas".

Under a "common Eduktflüssigkeitszufuhr "within the meaning of the present Invention is to be understood as any kind of supply in which at least a starting material liquid at least two spatially connected reaction spaces supplied is, in such a way that at least two reaction spaces of at least an educt liquid at the same time and are jointly exposed. The reaction space is in this case preferably a gas-liquid-solid reactor. The common educt fluid supply is preferably in addition in addition to the common Eduktzufuhr disclosed above. A educt fluid supply is preferably used in multiphase reactions.

A "connection", feeder, connecting line, Supply line or discharge within the meaning of the present invention any means that provides fluidic communication between two Points inside the device allowed, and the outside (outside the device) with respect to the exchange of substances. Preferably, the Connection thereby fluid-tight, more preferably fluid-tight at high printing. More preferably, the connection is via the below described channels, pipes or capillaries.

The term "channel" in the sense of the present invention describes a connector passing through a body, preferably a solid body of any geometry, preferably a round body, a cuboid, a disk or a plate tion of two present on the body surface openings, which in particular allows the passage of a fluid through the body.

A "pipe" in the sense of the present Invention is a channel in which a continuous cavity is formed, and the geometry of the outside of the tube substantially the cavity defining geometry of the inside follows.

A "capillary" can essentially be regarded as a special case of a pipe, with the difference that in a capillary - according to the above Regarding "restrictors" given - certain Dimensions met have to be. A capillary in the sense of the present invention may be preferred at the same time act as a "link" and / or as a "restrictor".

Channel, Tube or capillary can in the present case have any geometry. Regarding the can be formed by channel, tube or capillary inside the cavity formed one over the length of channel, tube or capillary variable cross-sectional area or preferably a constant cross-sectional area.

Of the Inner cross-section can, for example, an oval, round or polygonal Outline with straight or curved connections between the vertices of the polygon. Preferred are a round or an equilateral polygonal cross section.

Under a "holding gas" (holding gas) in the For the purposes of the present invention, any gas is to be understood as having which the output sides of at least two reaction spaces via a common holding gas supply can be applied, so that the pressure in Reaction space opposite increased pressure without holding gas is.

When Holding gas can be used any gas or any gas mixture the one or more with the flowing from the reaction space products and the Materials of the device with which it comes into contact, does not react, or only reacts so that the reaction to be examined is not significantly impaired. An inert gas or an inert gas mixture is preferred as the holding gas used. Particularly preferred are nitrogen, as well as the noble gases of the Periodic Table of the Chemical Elements, as well as all Mixtures thereof.

Of the Purpose of the holding gas is volume fluctuations in the individual Reaction spaces at Presence of at least one non-volume-constant reaction in at least one of the reaction rooms to avoid or at least minimize. Without contact with a holding gas can volumetric fluctuations to "strike through" the reaction chamber exit side portion of the device.

Under a common "holding gas supply" is to be understood that each of the at least two spatially separate reaction chambers with the same holding gas supply connected is. It is about it also conceivable to use more than one holding gas supply, under the condition, that the reaction spaces and the holding gas supplies preferred in material connection stand.

Under a "control fluid" within the meaning of the present Invention is any gas or liquid, or mixture from this, to understand with which / the product flows at least two reaction spaces over one common control fluid supply can be applied.

When Regular fluid, any fluid or fluid mixture can be used, the one or more with the flowing from the reaction space products and the Materials of the device with which it comes into contact, does not react, or only reacts so that the reaction to be examined is not significantly impaired.

The Control fluid can be either liquid or gaseous. If the reactions in the reaction space are gas phase reactions, see above is preferred as a control fluid a control gas. Will in the reaction room a liquid phase reaction carried out, so a control liquid is preferred accordingly.

is the control fluid is a gas, the above disclosure applies in terms of of the holding gas accordingly. As inert liquids are water and solvent as well as higher viscosity or non-Newtonian fluids such as inert oils prefers. Supercritical Gases are for the Purposes of the present invention are also considered as liquids.

in the Contrary to the holding gas supply, which it has the task of possible volume fluctuations in the individual reaction chambers It is the task of the control fluid supply, the fluid flows through the individual reaction rooms together and at the same time to a given same value regulate (reaction space flow control), without doing the Pressure in the reaction chambers to change.

This is preferably achieved by setting a predetermined total control fluid flow (F ^R _ges ) in a mass flow controller of the control fluid supply. Due to the fact that in the control fluid supply between the mass flow controller and the plurality of spatially separated Compounds to the individual reaction chambers each preferably a restrictor is located, and the restrictors all have the same or similar flow resistance / resistances, the entire control fluid is divided in equal flows to the individual reaction chambers.

Becomes For example, in the mass flow controller of the control fluid supply Set flow of 1.5 l / h, and branches the Regelfluidzufuhr after the mass flow controller in three separate connections (with each a restrictor), which are divided into three spatially separated Lead reaction spaces, so results after each restrictor, a flow of about 0.5 l / h.

Regarding the so with the help of a mass flow controller, preferably with the help a thermal mass flow controller, adjusted flows consists in principle no restriction. Preferably, the flow of the control fluid is adjusted so that educt from the educt feed through the reaction spaces, or subsets thereof, flow can. Further, it is preferable that the flow of at least one control fluid 0.001% to 99.9% of the flow of at least one Eduktfluids, further preferably 95% to 0.01% thereof, more preferably 90% to 0.1 %. is the volume of reaction spaces 0.1 to 50 ml, so is in the context of the present invention Regelfluidflüsse of 0.5 to 10 l / h preferred.

There these rivers already "supplied" by the control fluid supply, as it were, decreases the flow to be supplied by the educt feed, and thus the flow through the reaction spaces, in each case by this amount. If a constant control fluid flow is set in the "start-up phase" described above, so can by raising or lowering this flow of control fluid, the flow of educt through the Each reactor can be lowered or increased without this the pressure in the reaction chambers significantly or at all impaired would.

Accordingly can by increasing (Decrease) of the control gas flow from the control fluid supply the educt flow be lowered (increased) in a gas phase reaction, and it can by Increase (Lowering) the control fluid flow from the control fluid supply the educt flow in a liquid phase reaction humiliated (increased) become.

All in all it is in this embodiment so possible, in a simple way, and in particular with a single one Mass flow controller, the amount of fluid flowing through all the reaction spaces even while to regulate the course of the parallel reactions, namely without significantly affecting the pressure prevailing in the reaction chambers to influence.

A "flow meter" in the sense of the present Invention is any component that controls the fluid flow, for example can measure the total gas flow of a holding gas. Such components are the expert as "flow indicator "(" FI "). which are based on a thermal process, are preferred.

A "pressure regulator" in the sense of the present invention is any component that measures the pressure of a fluid and, after Compare with a predetermined setpoint or threshold, adjust if necessary can. Such components are known to the skilled person as "pressure indicator control "(" PIC ") known.

Under a "mass flow controller" (mass flow controller) Within the meaning of the present invention, each measuring and control circuit by means of which the flow of a fluid is measured and, if necessary after comparison with a nominal value, set variably can be. A mass flow controller can act as an active restrictor be considered in the sense described above. A mass flow controller is the expert as "FIC" (flow indicator control). Mass flow controller in the sense of the present Invention can as well as liquids as well as for gases be used. Preference is given to such mass flow controllers used, which are based on a thermal measuring principle.

In preferred embodiments The present invention provides the device according to the invention and the inventive method for Removal of multicomponent mixtures from high-pressure reactors or used in high-pressure systems in which substance mixtures are processed are, for the most part in liquid Phase present. For the purposes of the present specification refers the term liquid-phase mixtures on fluids that are predominantly in liquid Phase present. It is not excluded that in the liquid phase mixture also a certain proportion of dispersed solids - such as Polymerization catalysts - included can be. The equipment in which the liquid-phase mixtures are processed are used as apparatuses for Liquid-phase systems designated.

For the purposes of the present invention, the term "separator" refers to an apparatus in which the liquid and gaseous components or two liquid components of the product fluid are at least partially separated from a reaction space., It is possible, especially on the low pressure side, for some to be light Volatile components remain in the liquid phase or even that some components of medium volatility in the respective gas phase to pass .. By means of the preferred method step of Stripping (which occurs by introducing inert / stripping gas into the liquid phase in the separator) allows volatile components to be almost completely transferred from the liquid phase to the gas phase.

The inventive device and the method according to the invention are preferably used in conjunction with test stands in the laboratory sector, preferably for testing catalysts.

With Help the device of the invention and the method according to the invention can carry out of catalytic test experiments in an improved manner be carried out in parallel. The reactions preferably carried out in parallel in the reactors can be the same or different.

Preferably can Reactions and analyzes made under continuous experimental conditions which causes fluctuations that are commonly associated occur with discontinuous operation, avoided or minimized. The quality of the analysis data is thus improved. About that can out also kinetic studies are carried out with a higher degree of resolution, there continuous product flows available for analysis stand. It is advantageous that the discharge of product fluid possible from the cycle times analyzers is decoupled. About that In addition, technical simplifications can be achieved since on a complex control mechanism for emptying the separator, such as this when using a discontinuous test apparatus is necessary, can be dispensed with.

From this also results in the preferred application of the invention to the Areas of high-throughput research and combinatorial chemistry. Particularly preferred, the invention in the study of Processes are applied, in which liquid and gaseous product fluids incurred together. In a preferred embodiment, the device and the method for continuous testing in connection with apparatus used for the testing of solid catalysts, which with a Fluid flow, in particular with a mixture of fluids (multicomponent mixture), be contacted.

Prefers includes the apparatus for testing solid catalysts Catalyst capacity (in the reaction chambers) in the range of 0.1 to 500 ml.

The relationship from the inner volume of the high pressure separator to the volume of the used Catalyst is preferably in a range from 10: 1 to 100: 1, where a ratio in a range of 20: 1 to 50: 1 is preferred.

The Internal volume of the rectification column - if the apparatus with Rectification is equipped - is preferably in one Range from 0.1 to 600 ml, with a range of 0.5 to 300 ml is preferred. The dimensioning of the internal volume of the rectification column is preferably determined by the range of LHSV with which the plant is operated.

On the low pressure side, this is done via the connection ( 84 ) conducted product fluid is preferably collected in collection containers. It is possible in a preferred embodiment of the method that the amount of product fluid obtained is determined gravimetrically.

Prefers The product fluid on the low pressure side is also a qualitative Subjected to analysis. Based on the analysis results can be essential Gain information that serves the effectiveness of catalyst materials or to determine properties of feed fluids as well as different ones To compare process conditions.

The High pressure side of the device and the low pressure side of the device can either separately heated or cooled. For this are appropriate, to use known in the art heating and / or cooling means.

In Regarding the design of the apparatus for a multiple reactor system Among other things, it is also important that the sizing the individual units of the device is known as accurately as possible. The concept of "sizing of Building units "refers Here, for example, on the length or the diameter of Lines, the internal volume and the shape of separators. In a preferred embodiment of the present invention are those within the device used (parallel) units respectively the same or similar Dimension (s) on. Especially in devices where only Among other things, small amounts of product fluids are to be handled also the adaptation of the individual system components of decisive Meaning for the high quality the achievable by the device performance.

The Residence times of the fluid in the separator should preferably be 2 to 100 times the residence times of the fluid in the reactor amount. Higher residence times are by no means excluded.

The inventive device can in different embodiments with or without rectification columns ( 80 ' ) and gas mixers ( 95 ) be equipped for product processing. When using the apparatus according to the invention in conjunction with hydrodesulphurisation ("hydrodesulphurisation"), preference may be given to the addition of rectification columns ( 80 ' ) are waived (see 1 ), since mainly H ₂ S is formed on highly volatile product fluids, which is already predominantly on the high-pressure side via the outlet line (FIG. 82 ) can be deducted for gases. Apart from that, it is often sufficient in such plants to check the recovery rate from the analysis of the liquid product fluid. With regard to the "material recovery" is on the relevant disclosure of the DE 10 2006 034 172 directed.

When using equipment in connection with gas separation on the low pressure side by rectification and the gas combination of the gases from the high pressure and the low pressure side via gas mixer (such as in the 2 and 3 shown), the components are to be adapted in their dimensions to the equipment conditions and the plant operation. Relevant parameters here are, for example, the plate number of the rectification column and the minimum size of the gas mixer.

It is preferred, the device according to the invention and the method according to the invention in connection with gas-to-liquid processes, Liquid-to-liquid processes (e.g., desulfurization, Denitrogenation) and liquid-to-gas processes (e.g., "hydrocracking or cracking ") to use. In Fischer-Tropsch reactions, gaseous educt fluids are used into the reaction chambers introduced, however, liquid and gaseous Product fluids are formed, which are investigated by means of the present apparatus can be.

In a preferred embodiment becomes the method according to the invention at least partially automated by means of a process control unit. In In a preferred embodiment, sequences may be used The individual process steps can also be repeated. In experimental apparatus, the having a plurality of reaction systems, the reaction systems can be sequentially, partially parallel or parallel by means of the device according to the invention be controlled.

According to one preferred embodiment Cleaning steps integrated into the process. purification steps preferably consist of, for example, that solvent or purge gas rinsed through parts of the device or that parts of the device are evacuated to prevent possible contamination to remove.

By the specification of process conditions (such as pressure, temperature) and / or by adapting apparative elements (such as Resistance value of restrictor elements) can be preferably both on the high pressure side and on the low pressure side the relative amounts of gaseous Components and liquid Influencing or controlling components in the product fluid.

10

supply unit for starting material

11

pressure regulator for starting material

12

common reactant supply

15

reaction space input side restrictors

20 '

reaction chamber

21

in the Reaction space located substance, preferably catalyst

25 '

Restrictors to the starting compound ( 82 )

27

connection (Reaction chamber restrictor multiport valve)

30

Multiport valve

40

connecting line to the analysis unit

41

Flowmeter

45

derivation

50

supply line for holding gas / holding gas supply

51

pressure regulator for holding gas

53 '

connection (Holding gas supply reaction gas derivation)

54

Node / mixing point

56

flow sensor

57

pressure sensor

60

supply unit for control fluid

61

Mass flow controller for control fluid

65

restrictors for control fluid supply

70

supply unit for educt liquid

71

Mass flow controller for educt liquid

72

common Eduktflüssigkeitszufuhr

73

Restrikoren the educt fluid supply

80

(High pressure) separator

80 '

rectification column

81

connection Reaction chamber separator

82

starting compound at the high-pressure separator

for the most part easy (he) volatile components

83

restrictor

83 '

connection to the receiving area / analysis area for less volatile fluids

84

connection to at least one low pressure area or low pressure separator (Output line of the high-pressure separator; "derivative")

85

Valve

87

(Manipulated) valve

91

Mass Flow Controller

92

Restriktorelement / or Valve

93

Stripgas- / inert gas

94

tempered Unit for gas mixer

95

gas mixer

96

gas supply (for stripping gas / inert gas)

97

gas discharge (for stripping gas / inert gas)

200 300, ...

pressure monitoring

201

optical monitoring (or measuring device)

202

PID controller

204

Valve to dosage of the cooling fluid

205

cooling section for capillaries

206

supply for cooling medium

210

check facility for decoupling the reactors

Claims (12)

Apparatus for continuously transferring and / or analyzing multicomponent mixtures, comprising at least the following components: (a) at least two parallel reaction spaces ( 20 ' ); (b) per reaction space ( 20 ' ) at least one reaction space exit-side compound ( 81 ) to at least one high-pressure separator ( 80 ); (c) per reaction space ( 20 ' ) at least one high-pressure separator ( 80 ); (d) per high-pressure separator ( 80 ) at least one compound ( 84 ) to at least one low-pressure region or to at least one low-pressure separator; (e) per high-pressure separator ( 80 ) at least one starting compound ( 82 ) for substantially gaseous compounds which form an analytical unit ( 40 ) leads; (f) in the reaction chamber outlet side high-pressure region, ie either between the outlet of the reaction chamber ( 20 ' ) and high-pressure separator ( 80 ) or at the high-pressure separator, in each case per unit "reaction space high-pressure separator", a connection to a (pressure) holding gas ( 50 ) and optionally a connection to a (pressure) control fluid ( 60 ), characterized in that each compound ( 84 ) at least one low-pressure region or low-pressure separator each have at least one restrictor ( 83 ) contains. Apparatus according to claim 1, characterized in that per separator ( 80 ) every connection ( 84 ) to a preferably with gas supply ( 96 ) and gas discharge ( 97 ) provided rectification column ( 80 ' ) leads. Device according to claim 2, characterized in that the device has at least one connection ( 83 ' ) from the rectification column ( 80 ' ) to at least one receiving area and / or analysis area for little volatile fluid (s). Apparatus according to claim 2 or 3, characterized in that this per reaction space ( 20 ' ) one of each low-pressure rectification column ( 80 ' ) outgoing gas line ( 97 ), which in each case with an associated high-pressure side gas outlet line ( 27 ) and in each case a gas mixer ( 95 ) is in operative connection, wherein the output line of the gas mixer preferably to an analysis unit ( 40 ) leads. Device according to one of the preceding claims, characterized in that the common holding gas supply ( 50 ) per reaction unit consisting of one reaction space each ( 20 ' ) and the reaction chamber on the output side holding gas supply each have its own pressure measuring device ( 200 . 300 , ...). Process for transferring product fluids from the high pressure region of at least two parallel reaction spaces ( 20 ) comprising at least the following steps: (i) separating at least one multicomponent mixture consisting of at least two parallel reaction spaces ( 20 ' ), in each case one associated with this high-pressure separator ( 80 ) which is in active connection ( 84 ) is at a low pressure area; (ii) transferring slightly volatile, substantially gaseous components of a product fluid via an exit line ( 82 ) for gaseous compounds of the respective high-pressure region of the high-pressure separator ( 80 ) to an analysis unit ( 40 ); (iii) transferring little (s) volatile components of a product fluid from the high pressure separator ( 80 ) via a high-pressure separator located on the bottom side, with restrictor ( 83 ) provided output line to a low pressure area ( 84 ). A method according to claim 6, characterized in that step (iii) is carried out so that during the transfer of product fluid, a state is established, in which at a pressure sensor, preferably at a pressure sensor for the holding gas supply ( 50 ) a cyclic and / or oscillatory pressure change is measurable. A method according to claim 6 or 7, characterized in that via the compound ( 84 ) on the bottom side discharged from the high-pressure separator product fluid via a rectification column ( 80 ' ) and is preferably rinsed with stripping gas / inert gas. A method according to claim 8, characterized in that the from the rectification column ( 80 ' ) exiting stripping gas with the respective from the exhaust pipe ( 82 . 27 ) gas is brought together and mixed, preferably in a gas mixer ( 95 ). A method according to claim 8 or 9, characterized in that in the gas mixer ( 95 ) combined gas to an analysis unit ( 40 ) is transferred. Method according to one of Claims 6-10, characterized that the transfer in step (iii) is continuous or largely continuous. Use of the device according to one of claims 1-5 or of the method according to any one of claims 6-11 for desulfurization, denitrogenation or for hydroprocessing or to study gas-to-liquid conversions.