EP2629886A2

EP2629886A2 - Device and method for testing catalysts with variable process pressure adjustment

Info

Publication number: EP2629886A2
Application number: EP11771033.5A
Authority: EP
Inventors: Armin Lange De Oliveira; Michael Dejmek; Oliver KÖCHEL; Jürgen BECHTEL
Original assignee: HTE GmbH; HTE GmbH the High Throughput Experimentation Co
Current assignee: HTE GmbH the High Throughput Experimentation Co
Priority date: 2010-10-22
Filing date: 2011-10-17
Publication date: 2013-08-28
Also published as: US20130273662A1; WO2012052149A3; WO2012052149A2; US9228985B2

Abstract

The present invention relates to a catalysis apparatus for testing catalysts with variable process pressure adjustment over a pressure range from 0.01 millibar to 300 bar. The device preferably has a multiplicity of reaction chambers (101, 102,...) which are arranged in parallel and the lines (211, 212,...) thereof at the reaction chamber outlet side are divided into two groups of sub-lines. One group of main lines (411, 412,...) is operatively connected to a regulating valve (61), which is common to all main lines, and to an exhaust air line (62), and the second group of secondary lines (311, 312, 313,...) and switching valves (321, 322,...) is operatively connected to an analysis unit (34). It is preferable for lines (201, 202,...) at the reaction chamber outlet side to be equipped in each case with a separate line for a supply of regulating fluid (211, 212,...). In a preferred embodiment, the connecting points of the lines (201, 202,...) at the reaction chamber outlet side to the respective main lines (411, 412,...) and secondary lines (311, 312,...) have in each case one mixing vessel (301, 302,...).

Description

The invention relates to a device and a method for the investigation of catalysts and for the optimization of process conditions. By means of the device according to the invention and the method according to the invention, it is possible to precisely adjust the internal pressure within the individual reaction chambers and also to vary them in a controlled manner. Characteristic of the device according to the invention is a division of the reaction chamber outlet-side lines into two subgroups of lines, the lines being in operative connection with control valves and / or switching valves.

The invention is particularly suitable for use in devices in which a plurality or a plurality of reactors are arranged in parallel. Thus, the invention is of particular importance in the field of high throughput research for the development of catalysts and for the optimization of process conditions. Numerous devices for the parallel testing of catalysts are known from the prior art. These devices often differ in complexity, which may vary depending on the specific technical requirements. The present invention is in principle in the field of device types equipped with a special process control system, as described in more detail, for example, in US Pat. No. 7,537,739 B2. This special process control system is inter alia also characterized in that the reactors arranged in parallel are equipped with a common pressure control gas supply and a common pressure maintenance gas supply. This makes it possible to create a series of operating parallel reactors under substantially equal pressure conditions - even if the reactions strong volume changes occur within the individual reactors. In EP 1 273 919 B1, Corma et al. a catalytic converter with a plurality of reactors arranged in parallel, in which the fluid lines, which are located downstream of the reactors, are divided into two different lines. The one group of discharges all lead to a common tank, wherein in each individual discharge a non-return valve is arranged. The non-return valves prevent pressure fluctuations, which occur, for example, within the tank, from being transferred to the reaction spaces. The check valves cause the individual lines and the associated reactors are decoupled from each other. One of the objects according to the invention is to provide a catalytic converter with the aid of which the process pressure adjustment can be implemented in as variable a manner as possible. At the same time the most accurate process pressure control within the reactors should be made possible and the apparatus should have a comparatively simple technical construction.

The objects mentioned here and further objects are achieved by providing a catalytic apparatus for the investigation of solid catalysts in a continuous process with at least one reaction space (101), a common educt fluid supply (01) and a reaction chamber exit-side conduit (201) marked that

(i) each reaction chamber exit-side line is in operative connection with a main line (411) and a secondary line (311),

(ii) the main line (411) is in operative connection with a control valve (61) and an exhaust line (62),

(iii) the secondary line (31 1) having a restrictor element (331) and a

Analyzer unit (34) is operatively connected. In a preferred embodiment, the connection line upstream of the restrictor element (331) has a switching valve (321).

In a further preferred embodiment of the apparatus according to the invention, each reaction chamber outlet-side line (201) is in operative connection with a line for regulating fluid supply (211).

In a further preferred embodiment, the connection point of reaction space outlet line (201), main line (41 1) and secondary line (311) comprises a mixing vessel and / or liquid phase separator (301).

In a preferred embodiment, the main conduit (50) is equipped with a pressurized gas supply line (50).

In a preferred embodiment, the catalytic converter according to the invention with a plurality or a multiplicity of reaction spaces (101, 102,...) With a common educt fluid supply (01) and a reaction chamber exit-side conduit (201, 202,...), Is characterized in that

(i) each reaction chamber exit-side line (201, 202, ...) is in operative connection with one main line (41 1, 412, 413,.

(ii) each of the main pipes (411, 412, 413, ...) is connected to a common exhaust pipe (62),

(iii) each secondary line is optionally in operative connection with its own switching valve (321, 322, 323,...) and is in operative connection with an analysis unit (34), wherein preferably in the individual operative connecting lines between the switching valve (321, 322, 323, ...) and analysis unit (34) in each case a restrictor element (331, 332, 333, ...) is present, and more preferably one or more multiport valves.

In a preferred embodiment, the apparatus according to the invention is characterized in that the connection points of the individual reaction chamber exit-side lines (201, 202,...) To the main lines (411, 412,. lines (31 1, 312, ...) each comprise a mixing vessel or a liquid phase separator (301, 302, 303, ...).

In a preferred embodiment of the apparatus according to the invention, each individual main line in each case has a feed line (401, 402, 403,...) For pressurized gas.

In a further preferred embodiment, each individual line of the educt fluid supply is provided with a preferably passive restrictor element. In a further preferred embodiment, the restrictor elements (331, 332, 333,...) Or (33) are micro-regulating valves. The control valves or micro-regulating valves must have a suitable setting range. Suitable adjustment range means that the adjustment range can be adapted to the prevailing pressure and the prevailing flow velocity, so that the flow can be changed by at least 5% (relative).

In a further preferred embodiment, the control valve (61) is a high-temperature control valve or consists of a cascade of control valves or high-temperature control valves.

The invention also relates to a method for the investigation of solid catalysts or for the optimization of process conditions by means of the catalytic converter according to the invention, wherein the educt fluid is simultaneously passed through a plurality of reaction spaces (101, 102,...) And the method is characterized in that

(A) the majority or the entire part of the product fluid from each individual reaction space (101, 102, ...) either completely through the respective main line (41 1, 412, ...) via a valve (61) in all Main lines (41 1, 412, ...) common exhaust duct (62) is passed, and / or

(b) at least a portion of the product fluid of a single or multiple

Reaction spaces through the standing with the respective reaction space in operative connection secondary line (311, 312, ...) to an analysis unit or a plurality of analysis lines (34) are passed, wherein the pressure in the individual reaction chambers by means of the control valve (61) is controlled.

The process according to the invention is preferably characterized in that it is used for the investigation of solid catalysts or for the optimization of process conditions, the process being carried out in a pressure range from 0 to 200 bar, preferably from 0 to 100 bar and more preferably from 0 to 30 bar , and preferably the pressure in this case can be varied continuously or discontinuously within the pressure range.

The process according to the invention is characterized in that the process is carried out at a reaction chamber internal temperature in the range from 20 to 1200 ° C., a temperature range from 50 to 800 ° C. is preferred, and a temperature range from 100 to 650 ° C. is particularly preferred.

The present invention also relates to a computer with a computer program product - or a processor-based control device such as a PLC - for controlling the catalytic converter according to the invention and for carrying out the method according to the invention.

Brief description of the figures:

Fig. 1 shows the schematic representation of an apparatus according to the invention with a single reactor (101), in which the reaction chamber output side line

(201) is divided into two sub-lines (411) and (311), wherein the sub-line (411) leads to the exhaust air and the sub-line (311) to the analysis unit (34). The exhaust air line (411) is provided with control valve (61) and the connecting line (311) to the analysis unit (34) is provided with switching valve (321) and flow restrictor or restriction (331).

Fig. 2 shows the schematic representation of an apparatus according to the invention with two parallel reactors (101, 102, ...), in which the with Analyzer unit (34) connected reaction chamber output side connecting lines (311) with a multiport valve (07) are in operative connection.

3 shows the schematic representation of an apparatus according to the invention with three reactors (101, 102,...) Arranged in parallel, in which the connection lines leading to the reaction chamber exit to mixing elements (301, 302,...) And in the lines to the analysis unit (34 ) no multiport valve is arranged.

Fig. 4 shows a schematic representation of an apparatus according to the invention with three parallel reactors (101, 102, ...), which corresponds to the device shown in Fig. 3, wherein the output lines (31 1, 312, 313) for the gaseous compounds via a single flow regulator or via a single throttle element (33) are guided. In Fig. 3 per gas line (301, 302, ...) each have their own throttle element is arranged.

Fig. 5 shows the schematic representation of the apparatus according to the invention, which is equipped with a single reactor (101), wherein in the illustration, the control devices for flow and pressure control are shown. The apparatus shown in the illustration is equipped with a pressurized gas supply. The pressure regulating fluid supply is not present in this embodiment.

Further details of the catalytic converter according to the invention are shown in the following part.

A feature of the catalytic converter according to the invention is also that the reaction chamber output-side lines (201, 202, ...) do not lead to a common damping container. Moreover, it is preferred that the connecting lines between the output sides of the reactors and the control valve (61) have no check valves. By means of the catalyst apparatus according to the invention, it is possible to keep the pressure conditions in the individual reactors during the performance of the catalytic experiments largely constant. In a preferred embodiment, the catalytic converter according to the invention has individual line regions, in which the diameters are increased in relation to the lines at the other points. For example, the extended diameter and enlarged volume regions have the function of a mixing section in which the pressurizing gas and the product fluid stream are thoroughly mixed. These regions are also referred to below as mixing containers (301, 302,...).

A mixing container according to the present invention preferably has at least twice the diameter as the line leading to the mixing container (301, 302, ...). Further preferably, a mixing container (301, 302, ...) at least a length to diameter ratio of two to one. It is further preferred that in the mixing vessel flow-breaking internals are included, such as Raschig rings, split, frits, broken granules or packing for distillation columns. It can also be used internals that correspond in their kind to the distillation columns, such as bubble cap.

In a further preferred embodiment of the catalytic converter according to the invention, the individual exhaust pipes (31 1, 312,...) Which lead to the analysis unit (34) are connected directly to the respective mixing vessels (301, 302,...). In this way, it is achieved that a very well mixed sample can be taken from the product fluid stream leaving the reactor.

The necessary provisions for sample mixing depend on the respective product spectrum and the process parameters in which the apparatus according to the invention is operated.

In a preferred embodiment, the apparatus according to the invention is operated as a gas-phase apparatus, which means that predominantly gaseous educt fluids are converted to predominantly gaseous product fluids. In the event that the catalytic converter apparatus is used for processes in which the product fluid stream also contains liquid constituents or constituents which can condense out under the given reaction conditions, the mixing vessel or the mixing vessels (301, 302, for pure mixing function also have the function of a separator or a collecting container (or collection containers) for liquid samples.

The exhaust lines leading to the analysis unit (311, 312,...) Are preferably connected in a manner to the mixing containers or separators, so that substantially only gaseous product fluid is removed from the separators.

In a further preferred embodiment, the mixing container or separator has the function of a damping container, which ensures that the pressure in the interior of lines and reactors during the gas removal does not change or only slightly. The gas is removed via the exhaust pipes (311, 312, ...) and serves to supply analysis gas to the analysis unit.

In a further embodiment of the catalytic device according to the invention, it is also possible to remove liquid sample from the separator or the separators. This can be done either via a common discharge valve for liquid and gaseous sample or two separate drain valves. In the latter case, the drain valve for liquid sample preferably acts on the bottom of the mixing container or separator. The effect on the floor is represented by the fact that the valve is located at the lower part of the container or that it is connected to a riser inside the container. By contrast, the gaseous sample discharge valve removes the gaseous sample from the gas space of the mixing vessel or separator in the outflow. With respect to the throttling elements (331, 332, 333, ...) in the exhaust pipes, it is preferred that these are passive or active restrictor elements. With the passive or set to a constant value active Restriktorelementen thus creates a control. In contrast, it is also possible for a control loop to be integrated in this plant area. This is realized by providing one or more flow sensors upstream or downstream of throttle elements or actuating elements (331, 332,...) Which act on the element (33). Preferably, the flow sensor is a mass flow sensor or a volume flow sensor.

The embodiment of the apparatus according to the invention ultimately also depends on the operating state in which the catalytic converter according to the invention is operated. Suitable passive restrictor elements are, for example, capillaries, pinhole diaphragms, microchannels or porous frits. The active throttle elements are preferably microvalves (fine regulating needle valves), mass flow controllers or even automated fine regulating valves. The automated fine regulating valves may, for example, be ReCO valves from Badger-Meter.

In the case where the apparatus has a hot gas analyzer as an analysis unit, it is possible to detect both the amount of gas sample taken and the composition. It is also possible that an accurate quantitative detection takes place by correcting the signal of the hot gas flow meter by the gas composition determined by means of the hot gas analyzer. It should be noted that the total product gas flow of the respective reactor is taken to determine an absolute flow rate. However, this also requires the separate supply of pressure-holding gas or additional pressure build-up gas into each individual exhaust gas line (see Figure 4, lines 401, 402, ...).

In a further embodiment, a predetermined amount of reference gas, which represents an internal standard and makes it possible to quantitatively detect the recovery rate of carrier gas or pressure build-up gas, is added to the fluid streams. This internal standard may be, for example, a certain proportion of argon gas. Due to the addition of a standard, it is not necessary to quantitatively detect the amount that is conveyed through the output lines (31 1, 312, ...) to the analysis unit. This can be advantageous, as a result of the measurement and control effort which would otherwise be required for the quantitative detection of gas flows and the associated balancing of the reaction.

The quantitative detection then takes place through the analysis of the gas flow. For example, when using argon gas as an internal standard, a gas chromatograph is used as an analysis unit equipped with a heat conductivity or helium ionization detector sensitive to argon. In the case of other fluids that serve as internal standards, other analytical methods are used accordingly. The configuration disclosed herein of a combination of a GC detector used with argon gas as a standard or tracer gas is exemplified herein. Any other possible combination of internal standard and a substance-specific detector can also be used. The main flow and the product fluid are supplied via a common control valve (61) of the exhaust air. By appropriate control of the control valve (61) and the back pressure regulator for the pressure hold gas (metered via line 50), the pressure can be controlled efficiently within the catalytic apparatus and within the individual reaction spaces. It should be emphasized as advantageous in the method and the apparatus of the present invention that in the present case the pressure can be regulated over a wider range than is possible with catalytic converters which are known in the prior art - as for example in US Pat. No. 7,537,739 B2.

The passive restrictors disclosed in US Pat. No. 7,537,739 B2 are fixed with regard to the flow resistance, so that a minimum pressure through the feed gas and a maximum pressure through the allowed dilution of the feed gas with pressurized gas are fixed.

According to the device according to the invention, the individual exhaust pipes (411, 412, 413, ...) are brought together in line (42), wherein the line (42) has a control valve (61) having a variable flow resistance. The variable control valve (61) assumes the function of the parallel arranged restrictors, which - according to the embodiment according to US 7,537,739 B2 - have a fixed flow resistance. By means of the apparatus according to the invention is a continuous pressure control over a range of a few millibars up to several hundred bar even without a reconstruction of the apparatus and the use of additional functional elements possible. In order to achieve target pressures that are below the atmospheric pressure, a vacuum pump (63) should be provided, as shown for example in FIG.

It should be emphasized that those embodiments of the apparatus according to the invention which are provided with a control fluid supply, that control fluid has no pressure regulating function. In this point, the apparatus according to the invention thus differs from those apparatus disclosed in WO 2005/063372 A2.

The design of the control valve (61) depends on the particular use of the catalytic converter and is in this case in no way limited. If the catalytic converter is connected to a large number of reactors, it is possible, and in this case preferred, for a plurality of control valves (61) to be arranged in parallel and for that valve to be actuated with the control range of the master value suitable for the present pressure regime or a group be controlled simultaneously by control valves, as this the pressure control range can be additionally increased in a simple manner.

An essential feature of the apparatus according to the invention is that the apparatus is provided with a pressure regulator. Preferably, the control valve (61) is controlled by a pressure regulator. The reaction chamber output-side line region is in this case in operative connection with a pressure sensor, wherein the controller determines its actual value on the basis of this pressure sensor. An example of such an arrangement is shown in FIG. Since the line with the control valve (61) is a main line, the pressure control is carried out in this embodiment of the apparatus via the main line. In a preferred embodiment, the pressure regulator receives its actual value from the line (42) or from the lines (411, 412, 413, ...). In a further and preferred embodiment, it is also possible that the pressure regulator is arranged in a bypass line. In this case, the pressure regulator acts on the control valve in the pressure hold gas line. For pressure control, it is crucial that the pressure regulator receives values from the system that are not altered by disruptive effects if possible.

In a special embodiment of the apparatus according to the invention, it is possible for one or more switchable restrictor elements to be connected in parallel to the line section with the variable restrictor element (331). The circuit takes place here by means of valves. The connection of restrictor elements has the advantage that the adjustment range of the variable restrictor element (331) can be adapted in stages to the experimental conditions, whereby this can preferably also be automated. Similarly, the adjustment range of the control valve (61) can be adjusted by connecting restrictor elements in parallel by means of valves.

The selection of the sampling valve depends on the respective application. It is possible that the control valves are used in exhaust gas streams whose temperature is in a range of 500 to 600 ° C. At the same time, it is possible to vary the pressures within the catalytic apparatus and within the individual reactors over a very wide range.

If the temperatures of the product fluid streams are in a temperature range of 500 to 600 ° C, then sensitive components of the apparatus can be exposed to a very high temperature load. The apparatus according to the invention thus also offers the advantage that the majority of the volume flow can be conducted via the lines to the control valve (61). The control valve is designed so that it is particularly suitable for high-temperature operation. A small part of the volume flow is passed through the output lines (311, 312, 313, ...), whereby the components (321, 322, 323, ...) exposed to a lower thermal load.

The direct removal of the product fluid stream compared to US 7,537,739 B2 has the further advantage that the sample is not diluted by pressure holding gas, so that the optimization of the sample analysis in the real composition of the Product fluid flow can take place and any dilution effects (reduction detection limit, etc.) must be disregarded.

The device according to the invention is preferably used for the investigation of catalysts in the laboratory or on a technical scale. The catalysts used for the investigations are preferably present as solids and the absorption capacity of the individual reaction space is preferably 0.1 g to 100 g of catalyst, more preferably the absorption capacity of the individual reaction space is 1 g to 50 g. The volume of the individual reaction space is preferably in a range from 0.1 ml to 150 ml, more preferably in a range from 1 ml to 100 ml and most preferably in a range from 5 ml to 50 ml.

The GHSV used for the tests is preferably in a range of 300 to 10,000 h ^-1 , preferably 500 to 3,000 h ^-1 , whereas the LHSV is in a range of 0.2 to 20 h ^-1 , preferably 0.5 to 10 h ^"1 .

The apparatus according to the invention can be operated in a pressure range from 0.01 bar to 200 bar, preferably the apparatus according to the invention is operated in a pressure range from 0.1 bar to 100 bar. (The pressures given here are based on the absolute pressures prevailing in the interior of the reaction spaces.) The apparatus can preferably be used for the investigation of reactions which are in a temperature range from 20 ° C to 1200 ° C, preferably from 50 ° C to 800 ° C, particularly preferred is a temperature range of 100 ° C to 650 ° C.

LIST OF REFERENCE NUMBERS

reactant supply

reaction spaces

reaction chamber output side lines

Control Fluid Supply (Dilution & Internal Standard)

mixing tank

second subgroup of reaction chamber exit side conduits switching valve

Flow controller or throttle elements

analysis unit

optional additional control fluid supply

first subset of reaction space output side lines

Connecting line or transfer line between

exhaust

pump

control valve

common exhaust pipe

Holding gas supply

Multiport valve

Flow regulator of the holding gas

Flow meter for material balance

Line to the analysis unit

Pressure regulator actuating valve (61)

Claims

claims

Catalyst apparatus for the investigation of solid catalysts in a continuous process, comprising at least one reaction space (101), a common educt fluid supply (01) and a reaction chamber exit-side conduit (201), characterized in that

(iii) the secondary line (31 1) is in operative connection with a restrictor element (331) and an analysis unit (34).

Catalyst apparatus for the investigation of solid catalysts according to claim 1, characterized in that the connecting line upstream of the restrictor element (331) has a switching valve (321).

Catalyst apparatus for the investigation of solid catalysts according to claim 1 or 2, characterized in that each reaction chamber outlet-side line (201) is in operative connection with a line for regulating fluid supply (21 1).

Catalyst apparatus for the investigation of solid catalysts according to one of the preceding claims, characterized in that a connection point of the reaction space exit line (201) with main line (41 1) and secondary line (311) comprises a mixing vessel and / or a liquid phase separator (301).

Catalyst apparatus for the investigation of solid catalysts according to one of the preceding claims, characterized in that the main line (50) is equipped with a supply line for pressurized gas (50).

Catalyst apparatus for the investigation of solid catalysts in a continuous process according to one of claims 1 to 5 having a plurality or plurality of reaction spaces (101, 102, ...) with a common Eduktfluidzufuhr (01) and a reaction chamber exit side line (201, 202, .. .), characterized in that

(i) each reaction chamber exit-side line (201, 202, ...) is in operative connection with one main line (411, 412, 413,.

(ii) each of the main lines (411, 412, 413, ...) is in operative connection with a common exhaust line (62),

(iii) each secondary line is optionally in operative connection with its own switching valve (321, 322, 323,...) and is in operative connection with an analysis unit (34), preferably into the individual operative connecting lines between the switching valve (321, 322, 323, ...) and the analysis unit (34) each have a restrictor element (331, 332, 333, ...), and more preferably one or more multiport valves.

Catalyst apparatus for the investigation of Feststpffkatalysatoren in a continuous process according to claim 6, characterized in that the connection points of the individual reaction chamber output side lines (201, 202, ...) with the main lines (41 1, 412, ...) and the secondary lines (311 , 312, ...) each comprise a mixing vessel or a liquid phase separator (301, 302, 303, ...).

Catalyst apparatus for the investigation of solid catalysts in a continuous process according to any one of claims 6 or 7, characterized in that each individual main line in each case has a feed line (401, 402, 403, ...) for pressure-holding gas.

9. A catalyst apparatus for the investigation of solid catalysts in a continuous process according to any one of claims 6 to 8, characterized in that each line of Eduktfluidzufuhr is provided with a single passive Restriktorelement.

10. A catalytic apparatus for the investigation of solid catalysts in a continuous process according to any one of claims 6 to 9, characterized in that the restrictor elements (331, 332, 333, ...) and (33) are micro-control valves or include.

1 1. A catalytic converter according to any one of the preceding claims, characterized in that the control valve (61) is a high-temperature control valve, or consists of a cascade of control valves or high-temperature control valves.

12. A method for the investigation of solid catalysts or for the optimization of process conditions by means of a catalytic apparatus according to one of claims 6 to 11, wherein the educt fluid is simultaneously passed through a plurality of reaction spaces (101, 102, ...) and the method is characterized that (a) predominant parts or the entire part of the product fluid from each individual reaction space (101, 102, ...) either completely through the respective main line (41 1, 412, ...) via a valve (61) in all Main lines (411, 412, ...) common exhaust duct (62) is passed, and / or

(B) at least a portion of the product fluid of a single or multiple reaction chambers through the standing with the respective reaction space auxiliary line (311, 312, ...) to an analysis unit or more analysis lines (34) are passed, the pressure in the individual Reaction spaces by means of the control valve (61) is controlled.

13. A method for the investigation of solid catalysts or for the optimization of process conditions by means of a catalytic apparatus according to claim 12, characterized in that the method in a pressure range of 0 to 200 bar, vor- preferably from 0 to 100 bar and more preferably from 0 to 30 bar is carried out, and the pressure in this case can be varied continuously or discontinuously within the pressure range.

Process for the investigation of solid catalysts or for the optimization of process conditions by means of a catalytic apparatus according to claim 12 or 13, characterized in that the process is carried out at a reaction chamber internal temperature in the range of 20 to 1200 ° C, preferably in a range of 50 to 800 ° C, and more preferably in a range of 100 to 650 ° C.

Computer with a computer program product for controlling a catalytic converter according to claims 1 to 11 and / or for carrying out a method according to claims 12 to 14.