Substance container for a chemical reaction

Abstract

Disclosed is a method for carrying out a chemical reaction in a reactor, at least one substance is present in a container that is closed in a gas-tight manner, is introduced into the reactor in said container and is released by breaking open the container. The container is designed such that it breaks open when a specified bursting pressure difference between the internal pressure and external pressure is exceeded. The container is broken open and the substance located in the container is thus released as a result of deliberate application in the reactor of a pressure difference exceeding the bursting pressure difference.

Claims

1. A method for carrying out a chemical reaction by reacting two or more substances in a reactor, in which at least one substance is present in a substantially reaction-inert container that is closed in a gas-tight manner, is introduced into the reactor in this container, and is released from the container by breaking open the container before or during the reaction, wherein a container is used that is designed such that it breaks open when a specified, known bursting pressure difference between the internal pressure and the pressure outside the container is exceeded, wherein the container is designed such that it breaks open at an external pressure higher than its internal pressure at least by the specified bursting pressure difference, and wherein the container is broken open and the substance located in the container is therefore released as a result of deliberate application in the reactor of a corresponding overpressure.

2. The method according to claim 1 wherein two or more identical substances are present in separate containers with different bursting pressure differences and are released selectively from the respective containers by deliberate application in the reactor of pressures adapted to the different bursting pressure differences.

3. The method according to claim 1, wherein two or more different substances are present in separate containers with different bursting pressure differences and are released selectively from the respective containers by deliberate application in the reactor of pressures adapted to the different bursting pressure differences.

4. The method according to claim 1, wherein the course of the reaction is controlled by selectively breaking open the container in a pressure-induced manner and by means of the resultant selective release of the substance or substances located in the containers.

5. The method according to claim 1, wherein all substances required for the reaction are introduced into the reactor before the start of the reaction, and wherein the substance or substances present in a container or in containers is or are released in accordance with a reaction plan by deliberately breaking open the container or the containers in a pressure-induced manner.

6. The method according to claim 1, wherein containers with graduated bursting pressure differences in the ranges of 1-10 bar, 10-30 bar, 30-70 bar or 70-200 bar are used.

7. The method according to claim 1, wherein at least one container is additionally used, which contains a substance that stops the chemical reaction, the specified bursting pressure difference of this container being higher than the specified bursting pressure difference of all other containers used, but being smaller than or at least not greater than a maximum pressure permissible for the respective reaction conditions.

8. A container, which is closed in a gas-tight manner and contains a measured quantity of a chemical substance, wherein the container is designed for a specified, known bursting pressure difference between the internal pressure and the pressure outside the container, such that it breaks open at an external pressure higher than its internal pressure at least by the specified bursting pressure difference, and wherein the container is broken open and the substance located in the container is therefore released as a result of deliberate application of a corresponding overpressure, and wherein information regarding the specified bursting pressure difference is assigned to said container.

9. The container according to claim 8, wherein the specified bursting pressure difference is determined by material selection, wall thickness, shaping and/or by predetermined breaking points.

10. The container according to claim 8, wherein the container is arranged within a casing container, and wherein the casing container is at least partially gas-permeable and/or liquid-permeable and is also designed such that it is not destroyed itself when the container located therein is broken open in a pressure-induced manner.

11. The container according to claim 10, wherein the casing container is equipped with at least one frit or a functionally equivalent element.

12. The container according to claim 10, wherein the casing container is equipped with at least one additional chamber containing a further chemical substance, said chamber being in gas communication and/or liquid communication via a fit or a functionally equivalent element with a chamber containing the container and being designed for a specified bursting pressure difference between the internal pressure and the pressure outside the casing container, such that it breaks open under pressure conditions that exceed the specified bursting pressure difference and releases the substance contained therein.

13. The container according to claim 8, wherein the information regarding the specified bursting pressure difference is assigned to said container by means of a marking, specifically in the form of a code or in the form of plain text, either on the container itself or on or in a container packaging.

14. A set of at least two containers according to claim 8.

15. The set according to claim 14, wherein it comprises containers with different substances, these containers being designed for identical and/or different bursting pressure differences.

16. The set according to claim 14, wherein it comprises containers with different substances, these containers being designed for different bursting pressure differences.

17. The set according to claim 14, wherein it comprises containers with identical substances, these containers being designed for different bursting pressure differences.

18. The set according to claim 14, wherein it comprises a plurality of containers, which differ by their specified bursting pressure difference and/or by the substances contained therein and/or by the quantities of the substances contained therein.

19. The set according to claim 14, wherein the information regarding the specified bursting pressure difference is assigned to the containers by means of a marking, specifically in the form of a code or in the form of plain text, either on the containers themselves or on or in a container packaging.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be described in greater detail hereinafter with reference to the accompanying drawings and on the basis of various exemplary embodiments. In the drawings:

(2) FIG. 1 shows a schematic illustration of an exemplary reactor that is open with four containers located therein, each containing a substance and still sealed in the gas-tight state,

(3) FIG. 2 shows a schematic illustration of the reactor in the closed state with containers located therein, one of said containers having already burst as a result of an application of pressure and having released the substance located therein,

(4) FIG. 3 shows a schematic illustration of the closed reactor with containers located therein, which have already all burst at a pressure greater compared to FIG. 2 and which have released the substances located therein,

(5) FIGS. 4a-g show simplified views of seven different embodiments of containers according to the invention containing a substance,

(6) FIGS. 5a-c show views of three further embodiments of containers according to the invention,

(7) FIGS. 6a-c show sectional illustrations of three further modified embodiments of containers according to the invention,

(8) FIG. 7 shows a simplified schema for illustrating a parallel reaction,

(9) FIG. 8 shows a basic sectional illustration of a flow reactor,

(10) FIG. 9 shows a simplified schema for explaining a Split & Pool method, and

(11) FIG. 10 shows a sketch explaining a set of containers according to the invention.

DESCRIPTION OF THE INVENTION

(12) The following definition applies for the description below: if reference signs are specified in a figure for the purposes of clarifying the drawings, but are not mentioned in the part of the description related directly thereto, reference is made to the explanation of said reference signs in the preceding or subsequent parts of the description. Conversely, in order to avoid an overload of the drawings for immediate comprehension, reference signs of lesser relevance are not shown in all figures. To this end, reference is made to the other figures.

(13) A conventionally introduced liquid substance S0 and four containers 1-4 still closed in a gas-tight manner for the time being are located in an exemplary reactor R illustrated in the open state in FIG. 1, wherein the container 1 for example contains a liquid substance S1, the container 2 contains a gaseous substance S2, and the containers 3 and 4 each contain a solid substance S3. The substance in containers 3 and 4 is the same, but is provided in different (or the same) quantities. The volume parts of the containers 2-4 not occupied by the respective substance S2 or S3 are filled with an inert gas or with a gas or gas mixture that is otherwise compatible with the reaction to be carried out. Instead of just one container, a plurality of containers 1-4 can also be used for each of the three substances S1-S3, said containers together containing the substance quantity required for the reaction to be carried out. The solid, liquid and/or gaseous substances are the starting materials for the reaction to be carried out and also catalysts, starters, accelerators and/or inhibitors where necessary. The substance S0 may also have been introduced in one or more separate containers, which has/have been broken open in any way (for example also under a specific pressure) upon introduction into the reactor R or immediately thereafter. This will not be discussed in greater detail here. The substance S0 can also be omitted completely depending on the reaction to be carried out, that is to say that all substances necessary for the reaction are present at the start in containers that are initially still closed. Furthermore, a gas can also be applied and the reaction can be carried out therein, and the gas may for example even itself be a further component required for the reaction (for example propylene gas in polyolefin syntheses).

(14) Containers 1-4 consist of a reaction-inert material, typically glass. The containers are produced, filled with substance and closed so as to be gas-tight in a manner known per se for example as is described in detail in the document WO 02/13969 A1 cited in the introduction. A laser device is preferably used to melt containers having very thin walls.

(15) The containers 1-4 are designed by the manufacturer for different specified bursting pressure differences by means of a suitable material selection, dimensioning of the wall thicknesses, shaping and, where necessary, also by predetermined breaking points. That which is to be understood by this has already been discussed in detail further above.

(16) Once the reactor is closed, as illustrated in FIG. 2, it is acted on by a gas or gas mixture suitable or required for the reaction to be carried out. The gas or gas mixture is fed in a manner known per se by means of a preferably computer-controlled pressure controller P from a gas storage container G.

(17) Alternatively, if the reaction allows or even requires, the temperature can also be increased. The pressure is likewise increased continuously, for example by means of evaporating solvent, and is controlled relatively accurately via the temperature/pressure curve.

(18) A pressure state (overpressure), which is sufficient to selectively cause the container (or the containers) having the lowest specified bursting pressure difference to burst, the other containers with higher bursting pressure differences not being damaged however during this process, is then produced deliberately in the reactor by means of the pressure controller P, either immediately at the start or at another desired moment in time, for example predefined by a reaction plan. In FIG. 2, the container 1 has been broken open in this way and the substance S1 contained therein released. The fragments of the container produced when the container 1 breaks open (bursts) are denoted in FIG. 2 by 1b.

(19) As the course of the reaction continues, the remaining containers are also broken open in the same way, gradually and selectively by deliberate application of pressure of sufficient magnitude, and the substances located therein are released, such that they can take part in the reaction or can influence the reaction. The end state is illustrated in FIG. 3, in which all containers have been broken open. The fragments of containers 1-4 are denoted here by 1b, 2b, 3b and 4b.

(20) A representative example of a reaction carried out in accordance with the method according to the invention is a polyolefin synthesis with the following reaction control, wherein the reactor no longer has to be opened during the reaction and no further reagent or other substance apart from the pressure application necessary in any case, for example with ethylene gas (first monomer), has to be added:

(21) Step 1: the reactor is charged with 6 containers, of which the first two with the same first bursting pressure difference contain a co-catalyst (for example x mg or x*0.6 mg MAO), a third and a fourth container likewise with the same second (higher) bursting pressure difference contain a (primary) catalyst (for example x mg or x*0.2 mg), a fifth container with a yet higher third bursting pressure difference contains a second monomer (for example butadiene, in addition to the first monomer ethylene gas), and a sixth container again with a yet higher fourth bursting pressure difference contains a quenching substance (for example x*10 mg EtOH). (Here, the factor x is any number).

(22) Step 2: the reactor is acted on by the first monomer ethylene gas and the pressure is set for example to 10 bar.

(23) Step 3: the two first containers break open under the pressure of 10 bar and release the co-catalyst MAO into the reactor.

(24) Step 4: waiting for 2 minutes.

(25) Step 5: the pressure is increased to approximately 30 bar.

(26) Step 6: the third and the fourth container break open under the pressure of 30 bar and release the (primary) catalyst.

(27) Step 7: waiting for 5 minutes until the active catalyst (catalyst+co-catalyst) has formed.

(28) Step 8: the pressure is temporarily increased for 1 minute to approximately 45 bar.

(29) Step 9: the fifth container with the second monomer in a precisely determined, discrete quantity breaks open under the temporarily increased pressure of 45 bar and releases said second monomer into the reactor.

(30) Step 10: the pressure is reduced to 30 bar.

(31) Step 11: waiting for 60 minutes.

(32) Step 12: the pressure is temporarily increased to approximately 60 bar for approximately 1 minute.

(33) Step 13: the sixth container breaks open as a result of the pressure increased to 60 bar and releases the quenching substance contained therein. As a result, the reaction taking place is aborted (quenched) practically in an instant.

(34) Step 14: the pressure is reduced to ambient pressure and the method is continued in accordance with the standard procedure known per se.

(35) FIG. 7 schematically illustrates an exemplary parallel reaction with use of three reactors, which are denoted by R.sub.1, R.sub.2 and R.sub.3. Similarly to the example in FIGS. 1-3, the three reactors are acted on by reaction gas from a common gas source G, wherein the pressure of the reaction gas is controlled jointly by a pressure controller P for all three reactors. The same pressure conditions thus prevail in the three reactors.

(36) Similarly to the example in FIGS. 1-3, the reactors are initially charged (here for example) with three containers 41.sub.1, 42.sub.1, 43.sub.1 or 41.sub.2, 42.sub.2, 43.sub.2 or 43.sub.1, 43.sub.2, 43.sub.3 containing a substance (see the uppermost row of reactors). The pressure is then increased at a specific moment in time in all three reactors until one of the three containers breaks open in each case and releases into the reactor the substance contained therein (illustrated in the middle row of reactors). In a subsequent step, the pressure in all three reactors is again increased until a second of the three containers breaks open in each case (illustrated in the lowermost row of reactors). This procedure is continued until all containers have been broken open and the substances contained therein have been released.

(37) The advantages already described further above when carrying out parallel reactions are immediately evident. The scheduling problem is eliminated, since all reactors can be charged with substance containers already before the reactions, and the reactions can then be controlled easily in equal measure (by central pressure control) in all reactors, either at the same time or individually.

(38) FIGS. 4a-4g show various possible embodiments of containers 11-17 containing substances. For practical reasons, the containers are generally elongate (FIGS. 4a-4d and 4f-4g), but may also be spherical (FIG. 4e). The container 11 in FIG. 4a is cylindrical with two rounded ends. The container 12 in FIG. 4b is likewise cylindrical, but has a rounded end and a flat end. The container 13 in FIG. 4c is cylindrical with two flat ends or is rectangular with six planar walls. The container 14 in FIG. 4d is conical or pyramidal. The container 15 in FIG. 4e is spherical. The common feature of all containers 11-15 in FIGS. 4a-4e is that they have a substantially constant or homogeneous wall thickness, which also determines their bursting pressure difference, wherein shapes with flat wall parts or sharp edges with otherwise constant structure of the walls generally have a lower bursting pressure difference than shapes with round surfaces and rounded ends. This enables different bursting pressure differences to be implemented in a simple manner. Depending on the desired specified bursting pressure difference, typical wall thicknesses range from 0.03 mm to approximately 2 mm, wherein (with the construction material glass) a bursting pressure difference range from a few bar up to more than 100-150 bar and possibly even higher may be covered. Here, the size of the containers compared to the wall thickness also plays a role. With larger containers, the wall thickness for higher bursting pressure differences may be several mm. A typical container with a bursting pressure difference of approximately 6 bar has the design according to FIG. 4a, is in this case approximately 50 mm long, approximately 10 mm thick and has a wall thickness of approximately 0.05 mm.

(39) FIGS. 4f and 4g show two alternative containers 16 and 17 with larger wall thicknesses (approximately 0.2 mm), which are provided with one predetermined breaking point 16s (FIG. 4f) and a plurality of predetermined breaking points 17s (FIG. 4g). Without predetermined breaking points, these containers would break at pressure differences in the region of >100 bar. However, the predetermined breaking points are designed such that the containers already burst at substantially lower overpressures, for example of approximately 10 bar. Of course, any other, higher or lower bursting pressure difference can be set by means of a suitable design of the predetermined breaking points. The container 16 provided with just one centrally arranged predetermined breaking point 16s normally breaks into two halves. With a number of predetermined breaking points, as with container 17 in FIG. 4g, smaller fragments are produced with no cavities or no significant cavities, so that a substance is fed quickly or very quickly to the reaction medium when the container bursts. On the other hand, more or less temporary concentrations thus occur.

(40) FIG. 5a shows a specifically designed container 18. Externally, the container 18 has a similar design to the containers 16 and 17 in FIGS. 4f and 4g and also has predetermined breaking lines 18s. However, glass-encased steel pearls 18p are fused into the slightly thicker container wall and are distributed such that, once the container has burst, at least one (glass-encased) steel pearl is present in each fragment. The fragments can thus be removed easily from the reaction mass by means of a magnet, the filtration process that is otherwise conventional being eliminated.

(41) In the case of the containers 19 and 20 illustrated in FIGS. 5b and 5c, two and three containers 19a and 19b, and 20a, 20b and 20c are illustrated respectively, nested one inside the other, wherein the individual containers each contain different substances and are also each designed for different bursting pressure differences, such that the individual containers can also be broken open selectively in these variants. In FIG. 5c, the innermost container 20c for example has the greatest wall thickness and the outermost container 20a has the lowest wall thickness. Of course, these containers may also be formed with predetermined breaking points.

(42) FIGS. 6a and 6b show a further important modification of a substance container according to the invention. In this case, the actual container 21 or 22 containing the substance is arranged within a casing container 31 or 32. The casing container 31 or 32 is designed in terms of its stability such that, when the container 21 located therein is broken open in a pressure-induced manner, it is not destroyed itself. The casing container 31 or 32 is thus more stable than the container 21 or 22 located therein, that is to say it can withstand higher pressures compared to the relevant container 21 or 22, or withstands practically any pressure, because it is open and a pressure compensation can thus take place. As a result, the casing container (with sufficient stability) remains intact when the container located therein is broken open in a pressure-induced manner. The casing container 31 or 32 is gas-permeable and/or liquid-permeable in some regions. This can be implemented for example by a frit 31f or two integrated frits 32f. Instead of frits, functionally equivalent elements, such as a membrane, may also be provided, which allow an exchange of gas and/or liquid, but retain solid particles (exceeding a specific size), but also allow suspended solids below a specific size (for example nanoparticles) to pass through.

(43) The use of such substance containers has the advantage that, once the inner containers containing the substances have been destroyed in a pressure-induced manner, the fragments of said containers are retained in the casing container and can thus be removed easily from the reaction mass, such that an otherwise necessary filtration or other separation of the fragments is eliminated. Here, the substance, which is soluble or suspended in fine particles, is supplied through the frit to the reaction medium (and if need be vice versa).

(44) With substance containers equipped with diaphragms, noble metal catalysis processes can be carried out, wherein the product is not contaminated by the noble metal, and the noble metal can be easily recovered.

(45) If the inner containers contain a solid reaction carrier as a substance, yet a further advantage is provided in as much as the reaction then takes place within the casing container, that is to say virtually in a chemical cell. In the Split & Pool method, as already mentioned further above, dozens or hundreds of catalysts can thus be tested for example or dozens or hundreds of peptides can be synthesised for example. Here, the casing container is preferably provided with an engraved barcode, which provides information regarding the substances contained.

(46) A modification of a substance container similar to FIGS. 6a and 6b is illustrated in FIG. 6c, in which the casing container 33 is closed on all sides. The casing container 33 comprises a central cylindrical portion 33c and two dome-shaped end portions 33a and 33b. Two frits (or functionally equivalent elements) 33f, which divide the interior of the casing container into three chambers, which are in gas and/or liquid communication via the frits, are located at the two ends of the central portion. The chamber formed by the central portion 33c receives a container 23 that can be broken open by means of deliberate pressure application. In each of the two chambers formed by the dome-shaped portions 33a and 33b a further substance S5 or S6, respectively, is located, which reacts with the substance S7 located in the inner container 23 when said substance S7 is released as the inner container is broken open in a pressure-induced manner, without contact with the reaction medium in the reactor. This substance container thus forms a de facto independent (sub-) reactor. By use of a plurality of such sub-reactors with different contents, different reactions can be carried out in parallel, more specifically for example all together in a correspondingly large reactor. Split & Pool reactions can thus be carried out in a thoroughly new manner and for thoroughly new reactions. The casing container 33 is also designed such that the two dome-shaped end portions 33a and 33b can be broken open by means of pressure application, similarly to the inner container 23, wherein the central portion 33c of the casing container (together with the frits 33f) remains intact however. It is then possible for the reaction mixture produced in the casing container to mix with the reaction mixture in the reactor, as is the case for example with the container in FIG. 6b.

(47) In a further modification, two or more substance containers may also be arranged within common casing containers.

(48) A container equipped with a casing container similarly to that in FIG. 6b can be used particularly advantageously to carry out reactions in a flow reactor, as is illustrated schematically by way of example with reference to FIG. 8.

(49) A flow reactor denoted as a whole by 60 comprises a substantially tubular reaction chamber 60a, which is looped via two line connections 60b into a reaction gas flow symbolised by arrows 60s. A casing container 50, which is cylindrical for example and is closed at its two ends for example by frits 50f, such that reaction gas can flow through it, is located in the reaction chamber 60a. The casing container 50 has been introduced into the reaction chamber 60a through an access opening (not illustrated here) in said reaction chamber.

(50) Here, four containers 51-54 for example, each with a chemical substance, for example a reaction carrier or catalyst or co-catalyst, are located inside the casing container 50. Depending on the reaction to be carried out, the containers 51-54 are broken open at the same time or at different moments in time by means of one or more pressure surges or generally by means of a pressure increase of the reaction gas, and the reaction is thus initiated or influenced. The reaction product remains in the casing container 50, which is then removed again from the reaction chamber 60a at a given time.

(51) FIG. 9 illustrates schematically a simple example of what is known as a Split & Pool method, in which casing containers of the previously described type are used as chemical cells.

(52) Here (in this example), four reactors R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are used. For example, four casing containers 71-74 similar to the casing container 50 shown in FIG. 8 with one or more substance containers, which are illustrated here in the state already broken open, are located in the first reactor R.sub.11. A substance W is fed to the reactor. Before the reaction with the substance W, a forming polymer for example, which (inter alia) contains molecules V, is located in the casing containers 71-74. Such an individual casing container is illustrated separately in FIG. 9 and is denoted by 70. Due to the reaction in the reactor R.sub.11, a molecule W is incorporated into the polymer, such that the polymers in the casing containers 71-74 ultimately contain all molecules V and W.

(53) In the next step, the four casing containers 71-74 are divided between the two reactors R.sub.12 and R.sub.13, wherein the casing containers 71 and 72 are introduced into the rector R.sub.12 and the casing containers 73 and 74 are introduced into the reactor R.sub.13. Different substances X and Y are supplied to the two reactors and are incorporated into the polymers in the respective casing containers 71-72 and 73-74, such that the casing containers 71-72 ultimately contain polymers with the molecules V, W and X and the casing containers 73-74 ultimately contain polymers with the molecules V, W and Y. The division of the casing containers between the two reactors R.sub.12 and R.sub.13 (or generally a plurality of reactors) is generally referred to as splitting.

(54) In the next step, the casing containers 71-74 are again combined in a single reactor R.sub.14 (pooling), which may of course be physically identical to one of the other reactors, for example the reactor R.sub.11. This reactor is charged with a further substance Z, wherein polymers with the molecules V, W, X and Z are ultimately formed in the casing containers 71-72, and polymers with the molecules V, W, Y and Z are ultimately formed in the casing containers 73-74.

(55) Of course (as is known per se with Split & Pool methods), the casing containers can be divided and combined in a varied manner as desired, wherein practically any number of casing containers and practically any number of reactors can also be used.

(56) As already mentioned, a particularly important aspect of the invention lies in the provision of sets of containers containing substances. Such sets can also be referred to as a substance library. These sets may comprise different containers depending on the intended purpose (reactions to be carried out). Here, different means that the containers may vary in terms of the substances contained therein, in terms of the substance quantities, and in terms of the bursting pressure differences for which they are designed, as is illustrated in FIG. 10 in the form of a graph. Here, the number of identical containers can also be seen to a certain extent as a fourth dimension or fourth degree of freedom.

(57) FIG. 10 symbolises a set, of which the containers are filled with n different substances c.sub.1 . . . c.sub.n, wherein the respective filled quantities are graduated based on mole equivalents from 0.1 mmol . . . 5.0 mmol and the bursting pressure differences range from 6.5 bar . . . 60 bar. The illustrated quantity and pressure values are of course to be understood purely by way of example. As a specific example, a container 80 is illustrated, which contains a measured quantity of 2.0 mmol of the substance c.sub.3 and is designed for a bursting pressure difference of 45 bar. The possibility that individual, some, or all containers in the sets can be provided twice or more is not illustrated in the drawing.

(58) Of course, in the set symbolised in FIG. 10, not all possible coordinate points (combinations of a specific substance, a specific substance quantity and a specific bursting pressure difference) have to be occupied in practice. A specific substance can be present for example in different containers at different filled quantities, but with only one single bursting pressure difference value. For another substance, containers with identical substance quantities, but different bursting pressure difference values can be contained in the set. For yet another substance, containers with, for example, just two different bursting pressure differences and additionally, for example, three different filled quantities can be contained in the set. In the extreme case, a substance may also be represented in the set in just a single container in a single measured quantity and with a single specified bursting pressure difference value of the container.

(59) For practical application, it is advantageous if a set comprises containers with at least 2, better still at least 3, different bursting pressure difference values. Furthermore, it is advantageous in practice if a set contains containers in each case with at least 3, preferably 4 and more, filled quantity graduations, wherein the filled quantities can be graduated both gravimetrically and based on mole equivalents. The number of represented different substances is of course dependent on the reactions for which the set is to be used. Furthermore, it is advantageous in practice if at least 2-3, but preferably a much larger number, of containers are represented in the set, at least for the most frequently used substances and filled quantities.