EP2139598A1

EP2139598A1 - Method and device for the continuous transfer and analysis of fluids

Info

Publication number: EP2139598A1
Application number: EP07819167A
Authority: EP
Inventors: Andreas Christian Moeller; Theo Vergunst; Armin Brenner
Original assignee: HTE GmbH; HTE GmbH the High Throughput Experimentation Co
Current assignee: HTE GmbH the High Throughput Experimentation Co
Priority date: 2006-11-10
Filing date: 2007-10-19
Publication date: 2010-01-06
Also published as: DE102006053078A1; WO2008055585A1; WO2008055585B1

Abstract

The present invention relates to a method and device for the continuous transfer of fluid products from reaction chambers. The device contains an arrangement of at least two high-pressure separators which are both functionally connected to a low-pressure separator or low-pressure region. Each connection between high-pressure region and low-pressure region is equipped with a restrictor. In the preferred embodiments of the device, the low-pressure region side is equipped with a rectification column and the outgoing gas pipe from the rectification column is combined by a gas mixer into a single pipe with the gas pipe of the corresponding high-pressure side. In a preferred embodiment, the claimed method is carried out in conditions in 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.

Description

Apparatus and method for the continuous transfer and analysis of fluids

The present invention relates to an apparatus and a method for testing the reactivity of solid catalysts, which are preferably used for the characterization of multicomponent mixtures and for the optimization of reaction conditions. In the present case, it is preferable to analyze or process multicomponent mixtures which contain at least two incompletely miscible fluid phases. The multicomponent mixture is preferably a product fluid from a reaction space.

In a multitude of chemical processes, multicomponent mixtures are produced, which, for example, are to be transferred from process systems into analysis systems. Multi-component mixtures typically have to be subjected to separation steps or to a product work-up. Multicomponent mixtures are preferably separated in separators, wherein, for example, the liquid and the gas phase are separated from each other.

The device according to the invention and the method according to the invention are preferably used in conjunction with the investigation of petrochemical processes. These processes preferably include desulfurization (hydrodesulfurization) and denitrogenation (hydrodenitrogenation), preferably of oils, vacuum gas oils or diesel, as well as hydroprocessing (hydroprocessing, hydrotreating, hydrocracking), again preferably of oils and vacuum gas oils it is preferred that the device according to the invention and the method according to the invention are used for the investigation of gas-to-liquid conversions (eg Fischer-Tropsch processes). An overview of the technical field to which the present application relates is given, for example, in WO 2005/063372 and in DE 103 61 003 B3. These rights relate to apparatus for the parallelized testing of catalysts under high pressure, which produce multicomponent mixtures with components of different volatility. When the high-pressure multicomponent mixtures (product fluids) leave the reaction chambers, they are first collected in high-pressure separators, the particularly volatile components of the fluid being discharged via gas outlet 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.

It is therefore one of the objects of the invention to provide an apparatus and a method with which product fluids can be separated into volatile and less volatile components and, if possible, continuously supplied to different receiving areas or analytical units. '

Another object is to improve the susceptibility of the apparatus with respect to the mechanical strength of individual components. About that In addition, the method according to the invention should also be designed in such a way that the method can be carried out as semi-automatically or fully automatically as possible by means of a suitable process control.

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) at least one reaction chamber exit side per reaction space (20 ')

Connection (81) to at least one high-pressure separator (80);

(c) at least one high-pressure separator (80) per reaction space (20 ');

(d) at least one connection (84) per high-pressure separator (80) to at least one low-pressure region or to at least one low-pressure separator;

(e) at least one output connection (82) for substantially gaseous compounds leading to an analysis unit (40) per high-pressure separator (80);

(f) in the reaction chamber exit side high pressure region, i. either between the outlet of the reaction space (20 ') and high-pressure separator (80) or on the high-pressure separator, in each 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 connection (84) to at least one low-pressure region or low-pressure separator each contain at least one restrictor (83) and further preferably contains no valve. The restrictor (83) preferably allows the continuous removal of product fluid and allows the waiver 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.

In a further preferred embodiment, the device according to the invention has at least one further of the following components: (g) at least one connection (84) downstream of the restrictor

(83) on the low pressure side at least one rectification column (80 '), which is preferably equipped with gas supply line (96) and discharge (97);

(h) at least one compound (83 ') from the rectification column (80') to at least one receiving area and / or analytical area for less volatile fluids;

(I) per reaction space (20 ') one of the low-pressure side rectification column (80') outgoing gas line (97) which is in operative connection with an associated high-pressure side gas outlet line (27) and in each case a gas mixer (95), wherein the

Output line of the gas mixer (95) preferably leads to an analysis unit (40).

With the aid of the preferred components (h) or (h) and (i), it is possible in a preferred embodiment of the method according to the invention to continuously work up product fluid in countercurrent with an inert gas / stripping gas. This preferred embodiment is particularly suitable for applications in the "Hydroprocessing" area. In a preferred embodiment, a multiport valve (30) is located between the individual connections leading from the different gas mixers (95) to the analysis unit (40). The gas feed line (96) is preferably used for the supply of inert gas / stripping gas, the gas discharge (97) preferably for the derivation of the same.

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

In a preferred embodiment, the common holding gas supply (50) is constructed in such a way that it is operatively connected per reaction unit consisting of one reaction space and the holding gas supply mounted on the reaction chamber outlet side with one pressure measuring device per connection (82) (200, 300,...).

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

(I) separating at least one multicomponent mixture, which emerges from at least two parallel reaction chambers (20 '), in each case one associated high-pressure separator (80) which is in operative connection (84) with a low-pressure region and / or a low-pressure separator ;

(ii) transferring slightly volatile, substantially gaseous components of a product fluid via a gaseous compound starting compound (82) of the respective high-pressure section of the high-pressure separator (80) to an analysis unit (40); (iii) transferring low volatile components of a product fluid from the high pressure separator (80) to a low pressure region (84) via an outlet line provided with restrictor (83) at the bottom of the high pressure separator.

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 performed without the use of a valve in the exit conduit (84). 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.

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

(iv) passing the product fluid originating from the discharge line (84) of the high-pressure separator via a rectification column (80 '), which is preferably flushed with a stripping gas; (v) supplying the stripping gas leaving the rectification column (80 ') to a gas mixer (95) to combine the stripping gas with the more volatile product fluid originating from the starting compound of the high pressure section (82, 27);

(vi) feeding the gases combined in the gas mixer (95) to a gaseous component analysis unit (40).

An operating mode, 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 base provided with restrictor element (83) attached outlet (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 is connected to the holding gas fluid supply (50).

The process according to the invention is therefore preferably carried out in a manner in which the (small) pressure fluctuations between the pressure rise and the pressure decrease, which are due to the manner of continuous fluid leakage through the restrictor element in the discharge of the separator, in a cyclical manner { "Oscillating").

The period of one cycle for minor pressure changes consisting of pressure increase and pressure drop is preferably in a range of 0.1 to 150 seconds per cycle, with a range of 2 to 80 seconds per cycle being more preferred. One cycle runs from the maximum pressure to the maximum pressure (end of the pressure increase) or from the minimum pressure to the minimum pressure (end of the pressure drop). This oscillating mode of operation is not found during operation of the device with valves on the product fluid output line of the high pressure separator and thus can not be expected. The surprising oscillating effect presumably results from the invention-specific combination of the device features (d) and (f), the present invention is not limited to this proposed mechanism.

Figure 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 in which pressure fluctuations occur in a cyclic or oscillatory form. The oscillatory signals indicate whether the process is running in a stable and / or desired state. In addition, the oscillatory signals can also be used specifically for process control, since a change of process parameters is usually recognizable by the change of the oscillatory signals.

In connection with the transfer of the fluid from the high-pressure separator into the low-pressure region, there is normally a relaxation of the fluid or of gaseous compounds dissolved in the liquid fluid, in which at least part of these volatile components pass into the gas phase. In order to remove as completely as possible the liquid product fluid from the volatile gaseous constituents, the liquid product fluid in a preferred embodiment passed through 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 shown for example in FIG.

In a preferred embodiment of the present invention, the gaseous components which exit on the low pressure side (84) and are withdrawn from the product fluid by rectification column (80 ') are fed with an inert gas / stripping gas via a gas outlet (97) at the top of the rectification column a gas mixer (95) passed. In the gas mixer, the gas stream coming from the low pressure side is preferably combined with the gaseous fluid coming directly from the gaseous compound outlet from the high pressure side (27) and supplied to an analysis unit (40).

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

For the purposes of the present invention, a "restrictor" is understood to mean any component which, when flowing through it with a fluid, represents a measurable flow resistance. "Measurable" means that the flow resistance of each restrictor is at least more than a factor of 2 by at least more than a factor of 5, more preferably around more than a factor of 10 is greater than the flow resistance of any other component (component) in the device, excluding other restrictors.

If restrictors are used on the reaction chamber side, then a pressure loss of at least 2 bar should preferably be generated in the process according to the invention, more preferably a pressure drop of at least 5 bar, more preferably of at least 10 bar. The pressure loss is the difference "pressure before the reaction space" '' 'minus the pressure after the reaction space.

If the restrictors are used on the reaction chamber outlet side, and if they serve in addition to the 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 in the process according to the invention a pressure drop of at least 10 bar is preferred preferably 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 the output side to the reaction chambers or subsets of reaction chambers belonging to such a set. Accordingly, the device according to the invention preferably comprises a set of restrictors, respectively the educt fluid or the Regelfluid- supply or the holding gas supply or the derivatives (84) are assigned for gaseous components. AIs restrictors in the context of the present invention are preferably metal plates with holes, sintered metal plates, pinholes, micromachined channels, capillaries and / or frits (porous materials, in particular sintered Keramikfπtten) to look at ("passive restrictors" Restrictors (15) in the reaction-chamber-inlet-side region should preferably control the flow of the inflowing fluid (10) and ensure a far-reaching uniform distribution of the inflowing fluids over the individual connections.

For the restrictors (83) in the lead (84), capillaries are preferred. The capillary diameter is preferably in a range from 5 to 250 μm, with a range from 10 to 150 μm being more preferred. 01 to 20 m, more preferably in a range of 0.1 to 10 m.

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

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.

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

In the event that the product entry rates in the separator (80) are significantly lower than the maximum possible discharge rates, usually predominantly gaseous fluid emerges from the bottom-side discharge line (84) provided with restrictor element (83), this gaseous fluid essentially consisting of the holding gas supply (50) and / or the Regelfluidzufuhr (60) stems. When larger amounts of product fluid are introduced into the separator (80), correspondingly smaller amounts of gaseous fluid emerge from the outlet (84) arranged on the bottom side.

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

When using (passive) restrictors (83) between the high pressure and low pressure ranges, these can be installed either in conjunction with a valve (87) or without a valve in the drain. In the event that a valve (87) is mounted upstream of the passive restrictor, it is possible that the transfer of product fluid during the process will be changed from the continuous to the discontinuous state by closing the valve. A discontinuous operating state can be desired, for example, when 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 discharge (84) of the bottom (low-pressure side) Abscheiderauslaufs each with at least one detector (201, 202, ...) is connected, 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 operation, the capillaries may have elevated temperatures. Because of these elevated capillary temperatures, it is advantageous to couple the photocell by means of optical fibers to an optics / electronics unit, so that it is not exposed to the elevated temperatures that prevail directly at the capillary. In addition to the use of optical sensors and a use of acoustic or dielectric sensors and vibration sensors is preferred.

With the aid of the aforementioned detectors, in addition to the possible slight pressure fluctuations within the high-pressure region of the system, it is possible to determine whether (essentially) gaseous fluid or (substantially) liquid product fluid flows through the line region at the position of the discharge at a particular point in time 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.

It is preferred that a detector element is selected whose response time is shorter than the cycle duration of a respective pressure fluctuation.

The more volatile, substantially gaseous fluids which are withdrawn from the high-pressure separator (80) and via the output connection (82) of a

Unit for analysis (40) are supplied, are also called hot gas or as Permanent gas called. 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 means of a suitable process control, in particular by restrictor dements (25 ') in the starting compound (82), the exit of gaseous components which have a lower volatility is largely prevented at this point, so that these components initially remain 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 method, the volatile gaseous components which are withdrawn via the connection (82) from the high-pressure region (80) are fed directly or via a multiport valve (36) to an analysis unit (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 easily volatile gaseous components already at the high-pressure separator 80, a downstream analysis unit connected to the low-pressure region is 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:

Fig. 1 shows a schematic representation of an apparatus with eight parallel reaction chambers (20 '), each of which is connected to a high-pressure separator (80) and subsequent low-pressure region (84). In the high-pressure separator (80) resulting gaseous

Components are provided with restrictors (25 ')

Derived compounds (82). The gases thus transferred are transferred via the

Connections (27) and a multiport valve (30) to an analysis unit (40) or to an output line (45) passed. in the

Low pressure area after the separator (80) are restrictors

(83).

FIG. 2 shows a schematic representation of an apparatus with eight reaction chambers (20 ') arranged in parallel, each of which has a combination of

Have high-pressure separator (80) and low pressure region, wherein the respective connecting line (84) on the low pressure side of a rectification (80 ') is downstream.

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

Fig. 4 shows a schematic representation of an apparatus with three reaction chambers, in which each individual connecting line (84) Capillaries from the high pressure side to the low pressure side is equipped with an optical monitoring unit (201, 301, 401).

5 shows a schematic representation of an apparatus with two reaction spaces, in which each connecting line (84) is provided with an optical measuring device (201), a PID controller (203), a valve for metering a cooling fluid (204) and a cooling section (205 ) to

Cooling of the capillary (83) is equipped.

In the following, essential technical terms as used in the present invention and as far as they do not directly follow from the technical knowledge will be explained.

For the purposes of the present invention, a "gas-phase reaction" is to be understood as meaning a chemical reaction in which all starting materials and products are present under the reaction conditions as gases.

A "liquid-phase reaction" in the context of the present invention is to be understood as meaning a chemical reaction in which all starting materials and products are liquid under reaction conditions.

For the purposes of the present invention, a "multiphase reaction" is to be understood as meaning a chemical reaction which takes place under reaction conditions in the presence of at least two different phases which are not completely miscible with one another. or solid and / or gaseous The phases may be starting materials or products or both The reactions to be investigated by the present apparatus may be gas phase, liquid phase or multiphase reactions. For the purposes of the present invention, the term "ultrafine component mixture" is understood to mean any mixture of at least two components which can be at least partially separated from one another by physical or physicochemical processes, or combinations thereof, in particular mixtures of at least two to understand incompletely miscible liquid phases or mixtures of at least one gaseous phase and at least one liquid phase and emulsions, dispersions or suspensions.

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 (for 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 or upstream of the high-pressure separator, in a range from 5 to 500 bar, preferably a pressure in the range from 20 to 250 bar and more preferably a pressure in the range from 90 to 150 bar The reactor and the high-pressure separator have no fixed upper limits, but the choice of specific materials and constructive features may give rise to a certain limit with regard to the upper pressure limit, which the person skilled in the art will recognize in consideration of the materials. For the purposes of the present invention, the term low pressure is to be understood as meaning a pressure which is lower than the pressure on the upstream side of a component (with respect to the reactant stream). The pressure on the low-pressure side of the device, ie preferably downstream of the high-pressure separator, is preferably at least 0.5 bar lower than the pressure on the high-pressure side of the device. The pressure on the low-pressure side is preferably in a range from 0 to 20 bar, more preferably in a range from 0 to 10 bar.

A "light (volatile) gaseous component" is preferably a gas which already exists in the high-pressure separator in the gaseous state or passes into this.

A "fluid" in the context of the present invention is any substance in which the elemental (molecular) constituents which make up the substance, for example elements or molecules, but also agglomerates thereof, move against one another, and in particular have no fixed long-range order to one another. These include, in particular, liquids or gases, but also waxes, oils, dispersions, fats, suspensions or melts If the medium is in liquid form, multiphase liquid systems are also understood as fluids.

For the purposes of the present invention, the term "valve" is to be understood as meaning any component which makes it possible to reduce a fluid flow, including bringing it to a standstill.

A "common educt feed" in the context 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 fed to the feed. at least one starting material are exposed. The common educt feed (12) is located in front of the reaction spaces (20 '),

For the purposes of the present invention, "reactant gas" means any gas or gas mixture which can be fed to the reaction spaces, or partial amounts thereof (via a common educt feed) The feed gas may, but need not, contain an inert gas and / or or an admixture which can serve as an internal standard for the determination of certain properties (for example gas flow etc.) The educt gas preferably contains at least one component which participates in the chemical reaction to be investigated, The educt may also contain liquid components.

For the purposes of the present invention, a "product" or "product fluid" means any fluid or fluid mixture and any disperse phase (which may optionally also contain solid constituents) which can be removed and analyzed from at least one reaction space. The product may or may not contain educt, but may or may not contain a fluid reaction product of the reaction which has taken place in a reaction space.

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

A "common educt liquid feed" in the sense of the present invention means any type of feed in which at least one educt liquid is fed to at least two spatially interconnected reaction spaces, specifically such that at least two reaction spaces are simultaneously and jointly exposed to the at least one feedstock liquid The reaction space in this case is preferably a gas-liquid-solid reactor. The common educt fluid supply is preferably additionally present in addition to the common educt feed disclosed above. An educt liquid feed is preferably used in multiphase reactions.

A "connection", supply, connection line, supply line or discharge in the sense of the present invention is any means which allows fluidic communication between two points within the device and which is closed to the outside (outside the device) with respect to the exchange of substances. In this case, the connection is preferably fluid-tight, more preferably fluid-tight, even at high pressures, and more preferably the connection is made via the channels, tubes or capillaries described below.

The term "channel" in the sense of the present invention describes a through a body, preferably a solid body of any geometry, preferably a round body, a cuboid, a disk or a plate, passing connection of two present on the body surface openings, in particular the passage of a Fluids allowed by the body.

A "tube" in the context of the present invention is a channel in which a continuous cavity is formed, and the geometry of the outside of the tube substantially follows the cavity-defining geometry of the inside.

A "capillary" can essentially be regarded as a special case of a tube, with the difference that in a capillary - according to the specifications given above with regard to "restrictors" - certain dimensions must be fulfilled. For the purposes of the present invention, a capillary may preferably simultaneously function as a "compound" and / or as a "restrictor".

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

The inner cross section may, for example, have 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.

A "hold gas" (holding gas) in the sense of the present invention is understood to mean any gas with which the output sides of at least two reaction spaces can be acted upon by a common holding gas supply, so that the pressure in the reaction space is increased in relation to the pressure without holding gas.

As a holding gas, any gas or gas mixture can be used which does not react with the products flowing from the reaction space and the materials of the device with which it comes into contact, or only so that the reaction under investigation does not significantly affect becomes. An inert gas or an inert gas mixture is preferably used as the holding gas. Particularly preferred are nitrogen, as well as the noble gases of the periodic table of the chemical elements, as well as all mixtures thereof.

The purpose of the holding gas is to avoid or at least minimize volume fluctuations in the individual reaction spaces in the presence of at least one non-volume-constant reaction in at least one of the reaction spaces. Without exposure to a holding gas volume fluctuations on the reaction chamber exit side part of the device can "break through". A common holding gas supply means that each of the at least two spatially separate reaction spaces is connected to the same holding gas supply It is also conceivable to use more than one holding gas supply, with the proviso that the reaction spaces and the holding gas feeds are preferred to be in connection with each other.

For the purposes of the present invention, a "control fluid" is understood to mean any gas or liquid, or any mixture thereof, with which the product flows from at least two reaction spaces can be acted upon by a common control fluid supply.

As a control fluid any fluid or fluid mixture may be used which does not react with or react with the products flowing from the reaction space and the materials of the device with which it comes into contact, so that the reaction to be examined does not substantially impair becomes.

The control fluid can be either liquid or gaseous. If the reactions in the reaction space are gas-phase reactions, a control gas is preferred as the control fluid. If a liquid-phase reaction is carried out in the reaction space, a control liquid is accordingly preferred.

If the control fluid is a gas, then the above-mentioned disclosure regarding the holding gas applies accordingly. As inert liquids, water and solvents as well as higher-viscosity or non-Newtonian liquids such as, for example, inert oils are preferred. Supercritical gases are also considered to be liquids for the purposes of the present invention.

In contrast to the holding gas supply, which has the task of compensating for possible volumene fluctuations in the individual reaction spaces, it is the

Task of the control fluid supply, the fluid flows through the individual reaction space together and at the same time to adjust to a predetermined same value (reaction space flow control), without changing the pressure in the reaction chambers.

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 case of the control fluid supply between the mass flow controller and the plurality of spatially separate connections to the individual reaction chambers, preferably one restrictor is located, and the restrictors all have the same or similar flow resistance / resistances, the entire control fluid in the same flows becomes divided into individual reaction rooms.

If, for example, a flow of 1.5 l / h is set in the mass flow controller of the control fluid supply, and the control fluid supply branches after the mass flow controller into three separate compounds (each having a restrictor), which lead to three spatially separate reaction spaces, this results after each Restrictor a flow of about 0.5 l / h.

With regard to the flows thus set with the aid of a mass flow controller, preferably with the aid of a thermal mass flow controller, there is in principle no restriction. Preferably, the flow of the control fluid is adjusted so that reactant can flow from the educt feed through the reaction spaces, or subsets thereof. It is further preferred that the flow of at least one control fluid is from 0.001% to 99.9% of the flow of at least one educt fluid, more preferably from 95% to 0.01% thereof, more preferably from 90% to 0.1%. If the volume of the reaction spaces is 0.1 to 50 ml, control fluid flows of 0.5 to 10 l / h are preferred for the purposes of the present invention.

Since these flows are already "provided" by the control fluid supply, as it were, the flow to be provided by the educt feed decreases, and allow the flow through the reaction chambers to increase by this amount. If a constant control fluid flow is set in the "start-up phase" described above, then by increasing or decreasing this control fluid flow, the flow of educt through the reactor can each be lowered or increased without the pressure in the reaction chambers being significantly or even impaired.

Accordingly, by increasing (decreasing) the control gas flow from the control fluid supply, the reactant flow in a gas phase reaction can be lowered (increased), and by increasing (decreasing) the control liquid flow from the control fluid supply, the reactant flow can be lowered (increased) in a liquid phase reaction.

Overall, in this embodiment, it is thus possible to regulate, in a simple manner, and in particular with a single mass flow controller, the amount of fluid flowing through all the reaction spaces, even during the course of the parallel reactions, without thereby significantly affecting the pressure prevailing in the reaction spaces to influence.

A "flow meter" in the sense of the present invention is any component which can measure the fluid flow, for example the total gas flow of a holding gas Such components are also known to the person skilled in the art as flow indicators ("FF"). Flowmeters based on a thermal process are preferred.

For the purposes of the present invention, a "pressure regulator" is any component which can measure the pressure of a fluid and, if necessary, adjust it after a predetermined setpoint or threshold value is known to those skilled in the art as "pressure indicator control"("P / C "). Under a, M ^ ssendurchfluss regulator ⁱⁱ (Mass Flow Controller) in the sense of the present invention, each measurement and control circuit is to be understood with the aid of measured which the flow of a fluid and, possibly after comparison with a desired value, can be set variably. A mass flow controller may be considered as an active restrictor in the sense described above. A mass flow controller is also known to the person skilled in the art as "flow indicator control." Mass flow controllers in the sense of the present invention can be used both for liquids and for gases based on a thermal measuring principle.

In preferred embodiments of the present invention, the device according to the invention and the method according to the invention are used for taking multicomponent mixtures from high-pressure reactors or from high-pressure systems in which mixtures of substances predominantly in the liquid phase are processed. For the purposes of the present specification, the term liquid-phase mixtures refers to fluids which are present predominantly in the liquid phase. It is not excluded that in the liquid phase mixture, a certain proportion of dispersed solids - such as polymerization catalysts - may be included. The apparatuses in which the liquid-phase mixtures are processed are referred to as liquid-phase systems.

For the purposes of the present invention, the term "separator" refers to a device in which the liquid and gaseous components or two liquid components of the product fluid are at least partially separated from a reaction space

Low pressure side - possible that some volatile components remain in the liquid phase or that some components of medium volatility in the respective gas phase to pass. By means of the preferred method step of stripping (which by introducing inert / Stripping gas in the liquid phase located in the separator) volatile components can be almost completely transferred from the liquid phase into the gas phase.

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

With the aid of the device according to the invention and the method according to the invention, the performance of catalytic test experiments can preferably be carried out in parallel in an improved manner. The reactions which are preferably carried out in parallel in the reactors may be the same or different.

Preferably, reactions and analyzes may be carried out under continuous experimental conditions, thereby avoiding or minimizing variations which may commonly occur in conjunction with discontinuous operation. The quality of the analysis data is thus improved. In addition, kinetic studies can be performed at a higher level of resolution, as product streams are continuously available for analysis. In this case, it is advantageous that the discharge of product fluid is decoupled from the cycle times of possible analyzers. In addition, technical simplifications can be achieved, as can be dispensed with a complex control mechanism for emptying the separator, as is necessary when using a discontinuous test apparatus.

This also results in the preferred application of the invention in the fields of high-throughput research and combinatorial chemistry. With particular preference, the invention can be used in the investigation of processes in which liquid and gaseous product fluids are used together. fall. In a preferred embodiment, the device and the method for continuous testing are used in conjunction with apparatuses for testing solid catalysts, which are contacted with a fluid stream, in particular with a mixture of fluids (multicomponent mixture).

Preferably, the apparatus for testing solid catalysts has a catalyst capacity (in the reaction spaces) ranging from 0.1 to 500 ml.

The ratio of the inner volume of the high-pressure separator to the volume of the catalyst used is preferably in a range of 10: 1 to 100: 1, with a ratio in a range of 20: 1 to 50: 1 being preferred.

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

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

Preferably, the product fluid is also subjected to a qualitative analysis on the low pressure side. Based on the analysis results, essential information can be obtained which serves to determine the effectiveness of catalyst materials or properties of feed fluids and to compare different process conditions. The high pressure side of the device and the low pressure side of the device may be selectively heated or cooled separately. For this purpose, appropriate, known in the art heating and / or cooling means to use.

With regard to the design of the device for a multiple reactor system, among other things, it is also important that the dimensioning of the individual structural units of the device is known as precisely as possible. As used herein, the term "unit dimensioning" refers to, for example, the length or diameter of conduits, the internal volume, and the shape of separators In a preferred embodiment of the present invention, the (parallel) assemblies used within the apparatus are the same or similar In particular, in devices in which only small amounts of product fluids are to be handled, among other things, the adaptation of the individual system components is of crucial importance for the high quality of the performance achievable by means of the device.

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

The device according to the invention can be equipped in different embodiments, optionally with or without rectification columns (80 ') and gas mixers (95) for product processing. When using the apparatus according to the invention in conjunction with hydrodesulphurization ("hydrodesulphurization"), it is preferably possible to dispense with the downstream of rectification columns (δθ ') (see FIG. 1), since H ₂ S, which predominantly forms on highly volatile product fluids For the most part, in such plants it is often sufficient to estimate the recovery rate from the analysis of the liquid product fluid to verify. With regard to the "return of substances", reference is made to the relevant disclosure content of DE 10 2006 034 172.

When using apparatuses in conjunction 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 (as shown for example in Figures 2 and 3), the components in their dimensions to the apparatus and conditions to adapt the plant operating mode. Relevant parameters here are, for example, the plate number of the rectification column and the minimum size of the gas mixer.

It is preferred that the device according to the invention and the method according to the invention are used in conjunction with gas-to-liquid processes, liquid-to-liquid processes (eg desulfurization, denitrogenation) and liquid-to-gas processes (eg hydrocracking or In Fischer-Tropsch reactions, gaseous educt fluids are introduced into the reaction spaces, but liquid and gaseous product fluids are formed, which can be investigated by means of the present apparatus.

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

According to a preferred embodiment, purification steps in the

Process flow integrated. Cleaning steps preferably consist of, for example, that solvent or purge gas through parts of the device be rinsed or that parts of the device are evacuated to remove possible contaminants.

By specifying process conditions (such as pressure, temperature) and / or by adapting apparatus elements (such as resistance of Restriktorelementen) 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.

LIST OF REFERENCE NUMBERS

10 - Supply unit for educt

11 - Pressure regulator for educt 12 - common educt feed

15 - Reaction room entrance-side restrictors

20 'reaction space

21 - substance in the reaction space, preferably catalyst 25 '- Restriction to the starting compound (82)

27 - connection (reaction space - restrictor - multiport valve)

30 - multiport valve

40 - Connecting line to the analysis unit

41 - Flow meter 45 - Discharge

50 - supply line for holding gas / holding gas supply

51 - Pressure regulator for holding gas

53 '- connection (holding gas supply - reaction gas discharge)

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 fluid

71 - Mass flow controller for educt liquid

72 - common educt fluid supply

73 - Restrictors of educt fluid supply 80 (high pressure) separator

80 'rectification column

81 connection reaction space separator

82 Output connection to the high-pressure separator for essentially light volatile components

83 Restrictor

83 'Connection to intake area / analysis area' for less volatile fluids

84 connection to at least one low-pressure area or low-pressure separator (outlet line of the high-pressure separator; "discharge")

85 valve

87 (adjusting) valve

91 mass flow controller

92 Restrictor element / or valve

93 stripping gas / inert gas feed

94 Tempered unit for gas mixer

95 gas mixer

96 gas supply line (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 for metering the cooling fluid

205 Cooling section for capillary

206 feed for cooling medium

210 Check device for decoupling the reactors

Claims

claims

1. An apparatus for continuous transfer and / or analysis of multicomponent mixtures, comprising at least the following components:

(a) at least two parallel reaction spaces (20 ');

(b) at least one reaction chamber outlet-side connection (81) to at least one high-pressure separator (80) per reaction space (20 ');

(c) at least one high-pressure separator (80) per reaction space (20 ');

(e) at least one output connection (82) for substantially gaseous compounds per high-pressure separator (80) leading to an analysis unit (40);

(f) in the reaction chamber exit side high pressure region, i. 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),

characterized in that each connection (84) to at least one

Low-pressure or low-pressure separator each containing at least one restrictor (83).

2. Apparatus according to claim 1, characterized in that per separator (80) each compound (84) to a preferably with gas supply line (96) and gas discharge (97) provided rectification column (80 ') leads.

3. A device according to claim 2, characterized in that the device has at least one compound (83 ') from the rectification column (80') to at least one receiving area and / or analysis area for little (he) volatile fluids.

4. Apparatus according to claim 2 or 3, characterized in that this comprises per reaction space (20 ') of each 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 preferably leads to an analysis unit (40).

5. Device according to one of the preceding claims, characterized in that the common holding gas supply (50) per reaction unit consisting of a respective reaction chamber (20 ') and the reaction chamber output side mounted holding gas supply each have its own pressure measuring device (200, 300, ...) grouted ,

6. A method for transferring product fluids from the high-pressure region of at least two parallel reaction spaces (20), which comprises at least the following steps:

(i) separating at least one multicomponent mixture emerging from at least two parallel reaction spaces (20 ') into a respective high-pressure separator (80) which is in operative connection with a low-pressure area (84); (ii) transferring slightly volatile, substantially gaseous components of a product fluid via a gaseous compound exit line (82) of the respective high pressure section of the high pressure separator (80) to an analysis unit (40); (iii) transfer of low volatile components of a

Product fluids from the high-pressure separator (80) via a bottom side, provided with restrictor (83) at the high-pressure separator to a low-pressure region (84).

7. The method according to claim 6, characterized in that step (iii) is carried out such 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 or oscillatory pressure change is measurable.

8. The method according to claim 6 or 7, characterized in that via the connection (84) on the bottom side discharged from the high-pressure separator product fluid via a rectification column (80 ') is passed and preferably flushed with stripping gas / inert gas.

9. The method according to claim 8, characterized in that from the rectification column (80 ') exiting stripping gas with the respective from the exhaust pipe (82, 27) of the high-pressure side gas is merged and mixed, preferably in a gas mixer (95).

10. The method according to claim 8 or 9, characterized in that in the gas mixer (95) combined gas is transferred to an analysis unit (40).

11. The method according to any one of claims 6-10, characterized in that the Überfuhren in step (iii) takes place continuously or substantially continuously.

12. Use of the device according to any one of claims 1-5 or the method according to any one of claims 6-11 for desulfurization, denitrogenation or for hydroprocessing or for the investigation of gas-to-liquid conversions.